Polyester Compositions Containing Cyclobutanediol Having a Certain Combination of Inherent Viscosity and Moderate Glass Transition Temperature and Articles Made Therefrom

ABSTRACT

Described are polyesters comprising (a) a dicarboxylic acid component comprising terephthalic acid residues; optionally, aromatic dicarboxylic acid residues or aliphatic dicarboxylic acid residues; 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and cyclohexanedimethanol residues. The polyesters may be manufactured into articles such as fibers, films, bottles or sheets.

CROSS-REFERENCES TO RELATED APPLICATIONS

This application is a continuation of application Ser. No. 11/391,565,entitled “Polyester Compositions Containing Cyclobutanediol Having aCertain Combination of Inherent Viscosity and Moderate Glass TransitionTemperature and Articles Made Therefrom” filed on Mar. 28, 2006, whichclaims the benefit of: U.S. Provisional Application Ser. No. 60/731,454filed on Oct. 28, 2005; U.S. Provisional Application Ser. No.60/731,389, filed on Oct. 28, 2005; U.S. Provisional Application Ser.No. 60/739,058, filed on Nov. 22, 2005; U.S. Provisional ApplicationSer. No. 60/738,869, filed on Nov. 22, 2005; U.S. ProvisionalApplication Ser. No. 60/750,692 filed on Dec. 15, 2005, U.S. ProvisionalApplication Ser. No. 60/750,693, filed on Dec. 15, 2005, U.S.Provisional Application Ser. No. 60/750,682, filed on Dec. 15, 2005, andU.S. Provisional Application Ser. No. 60/750,547, filed on Dec. 15,2005, U.S. application Ser. No. 11/390,672 filed on Mar. 28, 2006; U.S.application Ser. No. 11/390,752 filed on Mar. 28, 2006; U.S. applicationSer. No. 11/390,794 filed on Mar. 28, 2006; U.S. application Ser. No.11/391,565 filed on Mar. 28, 2006; U.S. application Ser. No. 11/390,671filed on Mar. 28, 2006; U.S. application Ser. N. 11/390,853 filed onMar. 28, 2006; U.S. application Ser. No. 11/390,631 filed on Mar. 28,2006; and U.S. application Ser. No. 11/390,655 filed on Mar. 28, 2006;U.S. application Ser. No. 11/391,125 filed on Mar. 28, 2006; U.S.application Ser. No. 11/390,751 filed Mar. 28, 2006; U.S. applicationSer. No. 11/390,955 filed Mar. 28, 2006; U.S. application Ser. No.11/390,827 filed Mar. 28, 2006; U.S. Application Ser. No. 60/786,572filed Mar. 28, 2006; U.S. Application Ser. No. 60/786,596 filed Mar. 28,2006; U.S. Application Ser. No. 60/786,547 filed Mar. 28, 2006; U.S.Application Ser. No. 60/786,571 filed Mar. 28, 2006; U.S. ApplicationSer. No. 60/786,598 filed Mar. 28, 2006; U.S. application Ser. No.11/390,883 filed Mar. 28, 2006; United States Application Ser. No.11/390,846 filed Mar. 28, 2006; U.S. application Ser. No. 11/390,809filed Mar. 28, 2006; U.S. application Ser. No. 11/390,812 filed Mar. 28,2006; U.S. application Ser. No. 11/391,124 filed Mar. 28, 2006; U.S.application Ser. No. 11/390,908 filed Mar. 28, 2006; U.S. applicationSer. No. 11/390,793 filed Mar. 28, 2006; U.S. application Ser. No.11/391,642 filed Mar. 28, 2006; U.S. application Ser. No. 11/390,826filed Mar. 28, 2006; U.S. application Ser. No. 11/390,563 filed Mar. 28,2006; U.S. application Ser. No. 11/390,847 filed Mar. 28, 2006; U.S.application Ser. No. 11/391,156 filed Mar. 28, 2006; U.S. applicationSer. No. 11/390,630 filed Mar. 28, 2006; U.S. application Ser. No.11/391,495 filed Mar. 28, 2006; U.S. application Ser. No. 11/391,576filed Mar. 28, 2006; U.S. application Ser. No. 11/390,858 filed Mar. 28,2006; U.S. a application Ser. No. 11/390,629 filed Mar. 28, 2006; U.S.application Ser. No. 11/391,485 filed Mar. 28, 2006; U.S. applicationSer. No. 11/390,811 filed Mar. 28, 2006; U.S. application Ser. No.11/390,750 filed Mar. 28, 2006; U.S. application Ser. No. 11/390,773filed Mar. 28, 2006; U.S. application Ser. No. 11/390,865 filed Mar. 28,2006; U.S. application Ser. No. 11/390,654 filed Mar. 28, 2006; U.S.application Ser. No. 11/390,882 filed Mar. 28, 2006; U.S. applicationSer. No. 11/390,836 filed Mar. 28, 2006; U.S. application Ser. No.11/391,063 filed Mar. 28, 2006; U.S. application Ser. No. 11/390,814filed Mar. 28, 2006; U.S. application Ser. No. 11/390,722 filed Mar. 28,2006; U.S. application Ser. No. 11/391,659 filed Mar. 28, 2006; U.S.application Ser. No. 11/391,137 filed Mar. 28,2006; U.S. applicationSer. No. 11/391,505 filed Mar. 28, 2006; U.S. application Ser. No.11/390,864 filed Mar. 28, 2006; U.S. application Ser. No. 11/391,571filed Mar. 28, 2006, all of which are hereby incorporated by thisreference in their entireties.

FIELD OF THE INVENTION

The present invention generally relates to polyester compositions madefrom terephthalic acid or an ester thereof or mixtures thereof;2,2,4,4-tetramethyl-1,3-cyclobutanediol; and cyclohexanedimethanol, thepolyester having a certain combination of inherent viscosity and glasstransition temperature (Tg). These compositions have a certaincombination of at least two of high impact strengths, moderate glasstransition temperature (Tg), toughness, certain inherent viscosities,low ductile-to-brittle transition temperatures, good color and clarity,low densities, chemical resistance, and long crystallization half-times,which allow them to be easily formed into articles.

BACKGROUND OF THE INVENTION

Poly(1,4-cyclohexylenedimethylene terephthalate) (PCT), a polyesterbased solely on terephthalic acid or an ester thereof and1,4-cyclohexanedimethanol, is known in the art and is commerciallyavailable. This polyester crystallizes rapidly upon cooling from themelt, making it very difficult to form amorphous articles by methodsknown in the art such as extrusion, injection molding, and the like. Inorder to slow down the crystallization rate of PCT, copolyesters can beprepared containing additional dicarboxylic acids or glycols such asisophthalic acid or ethylene glycol. These ethylene glycol- orisophthalic acid-modified PCTs are also known in the art and arecommercially available.

One common copolyester used to produce films, sheeting, and moldedarticles is made from terephthalic acid, 1,4-cyclohexanedimethanol, andethylene glycol. While these copolyesters are useful in many end-useapplications, they exhibit deficiencies in properties such as glasstransition temperature and impact strength when sufficient modifyingethylene glycol is included in the formulation to provide for longcrystallization half-times. For example, copolyesters made fromterephthalic acid, 1,4-cyclohexanedimethanol, and ethylene glycol withsufficiently long crystallization half-times can provide amorphousproducts that exhibit what is believed to be undesirably higherductile-to-brittle transition temperatures and lower glass transitiontemperatures than the compositions revealed herein.

The polycarbonate of 4,4′-isopropylidenediphenol (bisphenol Apolycarbonate) has been used as an alternative for polyesters known inthe art and is a well known engineering molding plastic. Bisphenol Apolycarbonate is a clear, high-performance plastic having good physicalproperties such as dimensional stability, high heat resistance, and goodimpact strength. Although bisphenol-A polycarbonate has many goodphysical properties, its relatively high melt viscosity leads to poormelt processability and the polycarbonate exhibits poor chemicalresistance. It is also difficult to thermoform.

Polymers containing 2,2,4,4-tetramethyl-1,3-cyclobutanediol have alsobeen generally described in the art. Generally, however, these polymersexhibit high inherent viscosities, high melt viscosities, and high glasstransition temperatures such that the equipment used in industry can beinsufficient to manufacture or post polymerization process thesematerials.

Thus, there is a need in the art for a polymer having a combination oftwo or more properties, chosen from at least one of the following:toughness, moderate glass transition temperatures (Tg), good impactstrength, hydrolytic stability, chemical resistance, longcrystallization half-times, low ductile to brittle transitiontemperatures, good color and clarity, lower density and/orthermoformability of polyesters while retaining processability on thestandard equipment used in the industry.

SUMMARY OF THE INVENTION

It is believed that certain compositions made from terephthalic acidresidues, an ester thereof, or mixtures thereof; cyclohexanedimethanol,an ester thereof, and mixtures thereof; and2,2,4,4-tetramethyl-1,3-cyclobutanediol with a certain combination ofinherent viscosities and/or glass transition temperatures are superiorto polyesters known in the art and to polycarbonate with respect to atleast one of the following: of high impact strengths, hydrolyticstability, toughness, chemical resistance, good color and clarity, longcrystallization half-times, low ductile to brittle transitiontemperatures, lower specific gravity and thermoformability. Thesecompositions are believed to be similar to polycarbonate in heatresistance and are still processable on the standard industry equipment.

In one aspect, the invention relates to a polyester compositioncomprising at least one polyester which comprises:

-   -   (a) a dicarboxylic acid component comprising:        -   i) 70 to 100 mole % of terephthalic acid residues;        -   ii) 0 to 30 mole % of aromatic dicarboxylic acid residues            having up to 20 carbon atoms; and        -   iii) 0 to 10 mole % of aliphatic dicarboxylic acid residues            having up to 16 carbon atoms; and    -   (b) a glycol component comprising:        -   i) 1 to 99 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol            residues; and        -   ii) 1 to 99 mole % of cyclohexanedimethanol residues,            wherein the total mole % of the dicarboxylic acid component            is 100 mole %, and the total mole % of the glycol component            is 100 mole %; and            wherein the inherent viscosity is 0.10 to less than 1.0 dL/g            as determined in 60/40 (wt/wt) phenol/tetrachloroethane at a            concentration of 0.25 g/50 ml at 25° C.; and            wherein the polyester has a Tg of 85 to 120° C.

In one aspect, the invention relates to a polyester compositioncomprising at least one polyester which comprises:

-   -   (a) a dicarboxylic acid component comprising:        -   i) 70 to 100 mole % of terephthalic acid residues;        -   ii) 0 to 30 mole % of aromatic dicarboxylic acid residues            having up to 20 carbon atoms; and        -   iii) 0 to 10 mole % of aliphatic dicarboxylic acid residues            having up to 16 carbon atoms; and    -   (b) a glycol component comprising:        -   i) 1 to 99 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol            residues; and        -   ii) 1 to 99 mole % of cyclohexanedimethanol residues,            wherein the total mole % of the dicarboxylic acid component            is 100 mole %, and

the total mole % of the glycol component is 100 mole %; and

wherein the inherent viscosity is 0.35 to less than 1.0 dL/g asdetermined in 60/40 (wt/wt) phenol/tetrachloroethane at a concentrationof 0.25 g/50 ml at 25° C.; andwherein the polyester has a Tg of 85 to 120° C.

In one aspect, the invention relates to a polyester compositioncomprising at least one polyester which comprises:

-   -   (a) a dicarboxylic acid component comprising:        -   i) 70 to 100 mole % of terephthalic acid residues;        -   ii) 0 to 30 mole % of aromatic dicarboxylic acid residues            having up to 20 carbon atoms; and        -   iii) 0 to 10 mole % of aliphatic dicarboxylic acid residues            having up to 16 carbon atoms; and    -   (b) a glycol component comprising:        -   i) 5 to less than 50 mole % of            2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and        -   ii) greater than 50 to 95 mole % of cyclohexanedimethanol            residues,            wherein the total mole % of the dicarboxylic acid component            is 100 mole %, and the total mole % of the glycol component            is 100 mole %; and            wherein the inherent viscosity of the polyester is from 0.50            to 1.2 dL/g as determined in 60/40 (wt/wt)            phenol/tetrachloroethane at a concentration of 0.25 g/50 ml            at 25° C.; and            wherein the polyester has a Tg of 85 to 125° C.

In one aspect, the invention relates to a polyester compositioncomprising at least one polyester which comprises:

-   -   (a) a dicarboxylic acid component comprising:        -   i) 70 to 100 mole % of terephthalic acid residues;        -   ii) 0 to 30 mole % of aromatic dicarboxylic acid residues            having up to 20 carbon atoms; and        -   iii) 0 to 10 mole % of aliphatic dicarboxylic acid residues            having up to 16 carbon atoms; and    -   (b) a glycol component comprising:        -   i) 5 to less than 50 mole % of            2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and        -   ii) greater than 50 to 95 mole % of cyclohexanedimethanol            residues,            wherein the total mole % of the dicarboxylic acid component            is 100 mole %, and the total mole % of the glycol component            is 100 mole %; and            wherein the inherent viscosity of the polyester is from 0.50            to 1.2 dL/g as determined in 60/40 (wt/wt)            phenol/tetrachloroethane at a concentration of 0.25 g/50 ml            at 25° C.; and            wherein the polyester has a Tg of 85 to 120° C.

In one aspect, the invention relates to a polyester compositioncomprising at least one polyester which comprises:

-   -   (a) a dicarboxylic acid component comprising:        -   i) 70 to 100 mole % of terephthalic acid residues;        -   ii) 0 to 30 mole % of aromatic dicarboxylic acid residues            having up to 20 carbon atoms; and        -   iii) 0 to 10 mole % of aliphatic dicarboxylic acid residues            having up to 16 carbon atoms; and    -   (b) a glycol component comprising:        -   i) 10 to 30 mole % of            2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and        -   ii) 70 to 90 mole % of cyclohexanedimethanol residues,            wherein the total mole % of the dicarboxylic acid component            is 100 mole %, and the total mole % of the glycol component            is 100 mole %; and            wherein the inherent viscosity of the polyester is from 0.50            to 1.2 dL/g as determined in 60/40 (wt/wt)            phenol/tetrachloroethane at a concentration of 0.25 g/50 ml            at 25° C.; and            wherein the polyester has a Tg of 85 to 120° C.

In one aspect, the invention relates to a polyester compositioncomprising at least one polyester which comprises:

-   -   (a) a dicarboxylic acid component comprising:        -   i) 70 to 100 mole % of terephthalic acid residues;        -   ii) 0 to 30 mole % of aromatic dicarboxylic acid residues            having up to 20 carbon atoms; and        -   iii) 0 to 10 mole % of aliphatic dicarboxylic acid residues            having up to 16 carbon atoms; and    -   (b) a glycol component comprising:        -   i) 15 to 25 mole % of            2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and        -   ii) 75 to 85 mole % of cyclohexanedimethanol residues,            wherein the total mole % of the dicarboxylic acid component            is 100 mole %, and the total mole % of the glycol component            is 100 mole %; and            wherein the inherent viscosity is from 0.50 to 1.2 dL/g as            determined in 60/40 (wt/wt) phenol/tetrachloroethane at a            concentration of 0.25 g/50 ml at 25° C.; and            wherein the polyester has a Tg of 85 to 120° C.

In one aspect, the invention relates to a polyester compositioncomprising at least one polyester which comprises:

-   -   (a) a dicarboxylic acid component comprising:        -   i) 70 to 100 mole % of terephthalic acid residues;        -   ii) 0 to 30 mole % of aromatic dicarboxylic acid residues            having up to 20 carbon atoms; and        -   iii) 0 to 10 mole % of aliphatic dicarboxylic acid residues            having up to 16 carbon atoms; and    -   (b) a glycol component comprising:        -   i) 15 to 25 mole % of            2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and        -   ii) 75 to 85 mole % of cyclohexanedimethanol residues,            wherein the total mole % of the dicarboxylic acid component            is 100 mole %, and the total mole % of the glycol component            is 100 mole %; and            wherein the inherent viscosity is from 0.50 to 0.8 dL/g as            determined in 60/40 (wt/wt) phenol/tetrachloroethane at a            concentration of 0.25 g/50 ml at 25° C.; and            wherein the polyester has a Tg of 85 to 120° C.

In one aspect, the invention relates to a polyester compositioncomprising at least one polyester which comprises:

-   -   (a) a dicarboxylic acid component comprising:        -   i) 70 to 100 mole % of terephthalic acid residues;        -   ii) 0 to 30 mole % of aromatic dicarboxylic acid residues            having up to 20 carbon atoms; and        -   iii) 0 to 10 mole % of aliphatic dicarboxylic acid residues            having up to 16 carbon atoms; and    -   (b) a glycol component comprising:        -   i) 15 to 25 mole % of            2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and        -   ii) 75 to 85 mole % of cyclohexanedimethanol residues,            wherein the total mole % of the dicarboxylic acid component            is 100 mole %, and the total mole % of the glycol component            is 100 mole %; and            wherein the inherent viscosity is from 0.50 to 0.75 dL/g as            determined in 60/40 (wt/wt) phenol/tetrachloroethane at a            concentration of 0.25 g/50 ml at 25° C.; and            wherein the polyester has a Tg of 85 to 120° C.

In one aspect, the invention relates to a polyester compositioncomprising at least one polyester which comprises:

-   -   (a) a dicarboxylic acid component comprising:        -   i) 70 to 100 mole % of terephthalic acid residues;        -   ii) 0 to 30 mole % of aromatic dicarboxylic acid residues            having up to 20 carbon atoms; and        -   iii) 0 to 10 mole % of aliphatic dicarboxylic acid residues            having up to 16 carbon atoms; and    -   (b) a glycol component comprising:        -   i) 1 to 99 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol            residues; and        -   ii) 1 to 99 mole % of cyclohexanedimethanol residues,            wherein the total mole % of the dicarboxylic acid component            is 100 mole %, and the total mole % of the glycol component            is 100 mole %; and            wherein the inherent viscosity is from 0.35 to 1.2 dL/g as            determined in 60/40 (wt/wt) phenol/tetrachloroethane at a            concentration of 0.25 g/50 ml at 25° C.; and            wherein the polyester has a Tg of 100 to 120° C.

In one aspect, the invention relates to a polyester compositioncomprising at least one polyester which comprises:

-   -   (a) a dicarboxylic acid component comprising:        -   i) 70 to 100 mole % of terephthalic acid residues;        -   ii) 0 to 30 mole % of aromatic dicarboxylic acid residues            having up to 20 carbon atoms; and        -   iii) 0 to 10 mole % of aliphatic dicarboxylic acid residues            having up to 16 carbon atoms; and    -   (b) a glycol component comprising:        -   i) 15 to 25 mole % of            2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and        -   ii) 75 to 85 mole % of cyclohexanedimethanol residues,            wherein the total mole % of the dicarboxylic acid component            is 100 mole %, and the total mole % of the glycol component            is 100 mole %; and            wherein the inherent viscosity is from 0.50 to 1.2 dL/g as            determined in 60/40 (wt/wt) phenol/tetrachloroethane at a            concentration of 0.25 g/50 ml at 25° C.; and            wherein the polyester has a Tg of 100 to 120° C.

In one aspect, the invention relates to a polyester compositioncomprising at least one polyester which comprises:

-   -   (a) a dicarboxylic acid component comprising:        -   i) 70 to 100 mole % of terephthalic acid residues;        -   ii) 0 to 30 mole % of aromatic dicarboxylic acid residues            having up to 20 carbon atoms; and        -   iii) 0 to 10 mole % of aliphatic dicarboxylic acid residues            having up to 16 carbon atoms; and    -   (b) a glycol component comprising:        -   i) 15 to 25 mole % of            2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and        -   ii) 75 to 85 mole % of cyclohexanedimethanol residues,            wherein the total mole % of the dicarboxylic acid component            is 100 mole %, and the total mole % of the glycol component            is 100 mole %; and            wherein the inherent viscosity is from 0.50 to 0.8 dL/g as            determined in 60/40 (wt/wt) phenol/tetrachloroethane at a            concentration of 0.25 g/50 ml at 25° C.; and            wherein the polyester has a Tg of 100 to 120° C.

In one aspect, this invention relates to a polyester compositioncomprising at least one polyester which comprises:

-   -   (a) a dicarboxylic acid component comprising:        -   i) 70 to 100 mole % of terephthalic acid residues;        -   ii) 0 to 30 mole % of aromatic dicarboxylic acid residues            having up to 20 carbon atoms; and        -   iii) 0 to 10 mole % of aliphatic dicarboxylic acid residues            having up to 16 carbon atoms; and    -   (b) a glycol component comprising:        -   i) 5 to less than 50 mole % of            2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and        -   ii) greater than 50 to 95 mole % of cyclohexanedimethanol            residues,            wherein the total mole % of the dicarboxylic acid component            is 100 mole %, and the total mole % of the glycol component            is 100 mole %; and            wherein the inherent viscosity of the polyester is from 0.50            to 1.2 dL/g as determined in 60/40 (wt/wt)            phenol/tetrachloroethane at a concentration of 0.25 g/50 ml            at 25° C.; and wherein the polyester has a Tg of 95 to 115°            C.

In one aspect, the invention relates to a polyester compositioncomprising at least one polyester which comprises:

-   -   (a) a dicarboxylic acid component comprising:        -   i) 70 to 100 mole % of terephthalic acid residues;        -   ii) 0 to 30 mole % of aromatic dicarboxylic acid residues            having up to 20 carbon atoms; and        -   iii) 0 to 10 mole % of aliphatic dicarboxylic acid residues            having up to 16 carbon atoms; and    -   (b) a glycol component comprising:        -   i) 10 to 30 mole % of            2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and        -   ii) 70 to 90 mole % of cyclohexanedimethanol residues,            wherein the total mole % of the dicarboxylic acid component            is 100 mole %, and the total mole % of the glycol component            is 100 mole %; and            wherein the inherent viscosity of the polyester is from 0.50            to 1.2 dL/g as determined in 60/40 (wt/wt)            phenol/tetrachloroethane at a concentration of 0.25 g/50 ml            at 25° C.; and wherein the polyester has a Tg of 95 to 115°            C.

In one aspect, the invention relates to a polyester compositioncomprising at least one polyester which comprises:

-   -   (a) a dicarboxylic acid component comprising:        -   i) 70 to 100 mole % of terephthalic acid residues;        -   ii) 0 to 30 mole % of aromatic dicarboxylic acid residues            having up to 20 carbon atoms; and        -   iii) 0 to 10 mole % of aliphatic dicarboxylic acid residues            having up to 16 carbon atoms; and    -   (b) a glycol component comprising:        -   i) 15 to 25 mole % of            2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and        -   ii) 75 to 85 mole % of cyclohexanedimethanol residues,            wherein the total mole % of the dicarboxylic acid component            is 100 mole %, and the total mole % of the glycol component            is 100 mole %; and            wherein the inherent viscosity of the polyester is from 0.50            to 1.2 dL/g as determined in 60/40 (wt/wt)            phenol/tetrachloroethane at a concentration of 0.25 g/50 ml            at 25° C.; and wherein the polyester has a Tg of 95 to 115°            C.

In one aspect, this invention relates to a polyester compositioncomprising at least one polyester which comprises:

-   -   (a) a dicarboxylic acid component comprising:        -   i) 70 to 100 mole % of terephthalic acid residues;        -   ii) 0 to 30 mole % of aromatic dicarboxylic acid residues            having up to 20 carbon atoms; and        -   iii) 0 to 10 mole % of aliphatic dicarboxylic acid residues            having up to 16 carbon atoms; and    -   (b) a glycol component comprising:        -   i) 5 to less than 50 mole % of            2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and        -   ii) greater than 50 to 95 mole % of cyclohexanedimethanol            residues,            wherein the total mole % of the dicarboxylic acid component            is 100 mole %, and the total mole % of the glycol component            is 100 mole %; and            wherein the inherent viscosity of the polyester is from 0.50            to 0.75 dL/g as determined in 60/40 (wt/wt)            phenol/tetrachloroethane at a concentration of 0.25 g/50 ml            at 25° C.; and wherein the polyester has a Tg of 85 to 125°            C.

In one aspect, this invention relates to a polyester compositioncomprising at least one polyester which comprises:

-   -   (a) a dicarboxylic acid component comprising:        -   i) 70 to 100 mole % of terephthalic acid residues;        -   ii) 0 to 30 mole % of aromatic dicarboxylic acid residues            having up to 20 carbon atoms; and        -   iii) 0 to 10 mole % of aliphatic dicarboxylic acid residues            having up to 16 carbon atoms; and    -   (b) a glycol component comprising:        -   i) 5 to less than 50 mole % of            2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and        -   ii) greater than 50 to 95 mole % of cyclohexanedimethanol            residues,            wherein the total mole % of the dicarboxylic acid component            is 100 mole %, and the total mole % of the glycol component            is 100 mole %; and            wherein the inherent viscosity of the polyester is from 0.50            to less than 0.75 dL/g as determined in 60/40 (wt/wt)            phenol/tetrachloroethane at a concentration of 0.25 g/50 ml            at 25° C.; and wherein the polyester has a Tg of 85 to 120°            C.

In one aspect, this invention relates to a polyester compositioncomprising at least one polyester which comprises:

-   -   (a) a dicarboxylic acid component comprising:        -   i) 70 to 100 mole % of terephthalic acid residues;        -   ii) 0 to 30 mole % of aromatic dicarboxylic acid residues            having up to 20 carbon atoms; and        -   iii) 0 to 10 mole % of aliphatic dicarboxylic acid residues            having up to 16 carbon atoms; and    -   (b) a glycol component comprising:        -   i) 5 to less than 50 mole % of            2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and        -   ii) greater than 50 to 95 mole % of cyclohexanedimethanol            residues,            wherein the total mole % of the dicarboxylic acid component            is 100 mole %, and the total mole % of the glycol component            is 100 mole %; and            wherein the inherent viscosity of the polyester is from 0.50            to 0.75 dL/g as determined in 60/40 (wt/wt)            phenol/tetrachloroethane at a concentration of 0.25 g/50 ml            at 25° C.; and wherein the polyester has a Tg of 85 to 120°            C.

In one aspect, this invention relates to a polyester compositioncomprising at least one polyester which comprises:

-   -   (a) a dicarboxylic acid component comprising:        -   i) 70 to 100 mole % of terephthalic acid residues;        -   ii) 0 to 30 mole % of aromatic dicarboxylic acid residues            having up to 20 carbon atoms; and        -   iii) 0 to 10 mole % of aliphatic dicarboxylic acid residues            having up to 16 carbon atoms; and    -   (b) a glycol component comprising:        -   i) 5 to less than 50 mole % of            2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and        -   ii) greater than 50 to 95 mole % of cyclohexanedimethanol            residues,            wherein the total mole % of the dicarboxylic acid component            is 100 mole %, and the total mole % of the glycol component            is 100 mole %; and            wherein the inherent viscosity of the polyester is from 0.6            to 0.75 dL/g as determined in 60/40 (wt/wt)            phenol/tetrachloroethane at a concentration of 0.25 g/50 ml            at 25° C.; and wherein the polyester has a Tg of 85 to 120°            C.

In one aspect, this invention relates to a polyester compositioncomprising at least one polyester which comprises:

-   -   (a) a dicarboxylic acid component comprising:        -   i) 70 to 100 mole % of terephthalic acid residues;        -   ii) 0 to 30 mole % of aromatic dicarboxylic acid residues            having up to 20 carbon atoms; and        -   iii) 0 to 10 mole % of aliphatic dicarboxylic acid residues            having up to 16 carbon atoms; and    -   (b) a glycol component comprising:        -   i) 5 to less than 50 mole % of            2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and        -   ii) greater than 50 to 95 mole % of cyclohexanedimethanol            residues,            wherein the total mole % of the dicarboxylic acid component            is 100 mole %, and the total mole % of the glycol component            is 100 mole %; and            wherein the inherent viscosity of the polyester is from 0.65            to 0.75 dL/g as determined in 60/40 (wt/wt)            phenol/tetrachloroethane at a concentration of 0.25 g/50 ml            at 25° C.; and wherein the polyester has a Tg of 85 to 120°            C.

In one aspect, this invention relates to a polyester compositioncomprising at least one polyester which comprises:

-   -   (a) a dicarboxylic acid component comprising:        -   i) 70 to 100 mole % of terephthalic acid residues;        -   ii) 0 to 30 mole % of aromatic dicarboxylic acid residues            having up to 20 carbon atoms; and        -   iii) 0 to 10 mole % of aliphatic dicarboxylic acid residues            having up to 16 carbon atoms; and    -   (b) a glycol component comprising:        -   i) 5 to less than 50 mole % of            2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and        -   ii) greater than 50 to 95 mole % of cyclohexanedimethanol            residues,            wherein the total mole % of the dicarboxylic acid component            is 100 mole %, and the total mole % of the glycol component            is 100 mole %; and            wherein the inherent viscosity of the polyester is from 0.68            to 0.78 dL/g as determined in 60/40 (wt/wt)            phenol/tetrachloroethane at a concentration of 0.25 g/50 ml            at 25° C.; and wherein the polyester has a Tg of 85 to 120°            C.

In one aspect, this invention relates to a polyester compositioncomprising at least one polyester which comprises:

-   -   (a) a dicarboxylic acid component comprising:        -   i) 70 to 100 mole % of terephthalic acid residues;        -   ii) 0 to 30 mole % of aromatic dicarboxylic acid residues            having up to 20 carbon atoms; and        -   iii) 0 to 10 mole % of aliphatic dicarboxylic acid residues            having up to 16 carbon atoms; and    -   (b) a glycol component comprising:        -   i) 10 to 30 mole % of            2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and        -   ii) 70 to 90 mole % of cyclohexanedimethanol residues,            wherein the total mole % of the dicarboxylic acid component            is 100 mole %, and the total mole % of the glycol component            is 100 mole %; and            wherein the inherent viscosity of the polyester is from 0.50            to less than 0.75 dL/g as determined in 60/40 (wt/wt)            phenol/tetrachloroethane at a concentration of 0.25 g/50 ml            at 25° C.; and wherein the polyester has a Tg of 85 to 120°            C.

In one aspect, this invention relates to a polyester compositioncomprising at least one polyester which comprises:

-   -   (a) a dicarboxylic acid component comprising:        -   i) 70 to 100 mole % of terephthalic acid residues;        -   ii) 0 to 30 mole % of aromatic dicarboxylic acid residues            having up to 20 carbon atoms; and        -   iii) 0 to 10 mole % of aliphatic dicarboxylic acid residues            having up to 16 carbon atoms; and    -   (b) a glycol component comprising:        -   i) 10 to 30 mole % of            2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and        -   ii) 70 to 90 mole % of cyclohexanedimethanol residues,            wherein the total mole % of the dicarboxylic acid component            is 100 mole %, and the total mole % of the glycol component            is 100 mole %; and            wherein the inherent viscosity of the polyester is from 0.50            to 0.75 dL/g as determined in 60/40 (wt/wt)            phenol/tetrachloroethane at a concentration of 0.25 g/50 ml            at 25° C.; and wherein the polyester has a Tg of 85 to 120°            C.

In one aspect, this invention relates to a polyester compositioncomprising at least one polyester which comprises:

-   -   (a) a dicarboxylic acid component comprising:        -   i) 70 to 100 mole % of terephthalic acid residues;        -   ii) 0 to 30 mole % of aromatic dicarboxylic acid residues            having up to 20 carbon atoms; and        -   iii) 0 to 10 mole % of aliphatic dicarboxylic acid residues            having up to 16 carbon atoms; and    -   (b) a glycol component comprising:        -   i) 15 to 25 mole % of            2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and        -   ii) 75 to 85 mole % of cyclohexanedimethanol residues,            wherein the total mole % of the dicarboxylic acid component            is 100 mole %, and the total mole % of the glycol component            is 100 mole %; and            wherein the inherent viscosity of the polyester is from 0.50            to 0.75 dL/g as determined in 60/40 (wt/wt)            phenol/tetrachloroethane at a concentration of 0.25 g/50 ml            at 25° C.; and wherein the polyester has a Tg of 85 to 120°            C.

In one aspect, the invention relates to a polyester compositioncomprising at least one polyester which comprises:

-   -   (a) a dicarboxylic acid component comprising:        -   i) 70 to 100 mole % of terephthalic acid residues;        -   ii) 0 to 30 mole % of aromatic dicarboxylic acid residues            having up to 20 carbon atoms; and        -   iii) 0 to 10 mole % of aliphatic dicarboxylic acid residues            having up to 16 carbon atoms; and    -   (b) a glycol component comprising:        -   i) 15 to 25 mole % of            2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and        -   ii) 75 to 85 mole % of cyclohexanedimethanol residues,            wherein the total mole % of the dicarboxylic acid component            is 100 mole %, and the total mole % of the glycol component            is 100 mole %; and            wherein the inherent viscosity of the polyester is from 0.50            to less than 0.75 dL/g as determined in 60/40 (wt/wt)            phenol/tetrachloroethane at a concentration of 0.25 g/50 ml            at 25° C.; and wherein the polyester has a Tg of 85 to 120°            C.

In one aspect, the invention relates to a polyester compositioncomprising at least one polyester which comprises:

-   -   (a) a dicarboxylic acid component comprising:        -   i) 70 to 100 mole % of terephthalic acid residues;        -   ii) 0 to 30 mole % of aromatic dicarboxylic acid residues            having up to 20 carbon atoms; and        -   iii) 0 to 10 mole % of aliphatic dicarboxylic acid residues            having up to 16 carbon atoms; and    -   (b) a glycol component comprising:        -   i) 17 to 28 mole % of            2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and        -   ii) 72 to 83 mole % of cyclohexanedimethanol residues,            wherein the total mole % of the dicarboxylic acid component            is 100 mole %, and the total mole % of the glycol component            is 100 mole %; and            wherein the inherent viscosity of the polyester is from 0.65            to 0.75 dL/g as determined in 60/40 (wt/wt)            phenol/tetrachloroethane at a concentration of 0.25 g/50 ml            at 25° C.; and wherein the polyester has a Tg of 85 to 120°            C.

In one aspect, the invention relates to a polyester compositioncomprising at least one polyester which comprises:

-   -   (a) a dicarboxylic acid component comprising:        -   i) 70 to 100 mole % of terephthalic acid residues;        -   ii) 0 to 30 mole % of aromatic dicarboxylic acid residues            having up to 20 carbon atoms; and        -   iii) 0 to 10 mole % of aliphatic dicarboxylic acid residues            having up to 16 carbon atoms; and    -   (b) a glycol component comprising:        -   i) 15 to 25 mole % of            2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and        -   ii) 75 to 85 mole % of cyclohexanedimethanol residues,            wherein the total mole % of the dicarboxylic acid component            is 100 mole %, and the total mole % of the glycol component            is 100 mole %; and            wherein the inherent viscosity of the polyester is from 0.65            to 0.75 dL/g as determined in 60/40 (wt/wt)            phenol/tetrachloroethane at a concentration of 0.25 g/50 ml            at 25° C.; and wherein the polyester has a Tg of 100 to 120°            C.

In one aspect, the invention relates to a polyester compositioncomprising at least one polyester which comprises:

-   -   (a) a dicarboxylic acid component comprising:        -   i) 70 to 100 mole % of terephthalic acid residues;        -   ii) 0 to 30 mole % of aromatic dicarboxylic acid residues            having up to 20 carbon atoms; and        -   iii) 0 to 10 mole % of aliphatic dicarboxylic acid residues            having up to 16 carbon atoms; and    -   (b) a glycol component comprising:        -   i) 17 to 28 mole % of            2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and        -   ii) 72 to 83 mole % of cyclohexanedimethanol residues,            wherein the total mole % of the dicarboxylic acid component            is 100 mole %, and the total mole % of the glycol component            is 100 mole %; and            wherein the inherent viscosity of the polyester is from 0.7            to 0.8 dL/g as determined in 60/40 (wt/wt)            phenol/tetrachloroethane at a concentration of 0.25 g/50 ml            at 25° C.; and wherein the polyester has a Tg of 85 to 120°            C.

In one aspect, the invention relates to a polyester compositioncomprising at least one polyester which comprises:

-   -   (a) a dicarboxylic acid component comprising:        -   i) 70 to 100 mole % of terephthalic acid residues;        -   ii) 0 to 30 mole % of aromatic dicarboxylic acid residues            having up to 20 carbon atoms; and        -   iii) 0 to 10 mole % of aliphatic dicarboxylic acid residues            having up to 16 carbon atoms; and    -   (b) a glycol component comprising:        -   i) 17 to 28 mole % of            2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and        -   ii) 72 to 83 mole % of cyclohexanedimethanol residues,            wherein the total mole % of the dicarboxylic acid component            is 100 mole %, and the total mole % of the glycol component            is 100 mole %; and            wherein the inherent viscosity of the polyester is from 0.7            to 0.8 dL/g as determined in 60/40 (wt/wt)            phenol/tetrachloroethane at a concentration of 0.25 g/50 ml            at 25° C.; and wherein the polyester has a Tg of 100 to 120°            C.

In one aspect, the invention relates to a polyester compositioncomprising at least one polyester which comprises:

-   -   (a) a dicarboxylic acid component comprising:        -   i) 70 to 100 mole % of terephthalic acid residues;        -   ii) 0 to 30 mole % of aromatic dicarboxylic acid residues            having up to 20 carbon atoms; and        -   iii) 0 to 10 mole % of aliphatic dicarboxylic acid residues            having up to 16 carbon atoms; and    -   (b) a glycol component comprising:        -   i) 17 to 28 mole % of            2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and        -   ii) 75 to 85 mole % of cyclohexanedimethanol residues,            wherein the total mole % of the dicarboxylic acid component            is 100 mole %, and the total mole % of the glycol component            is 100 mole %; and            wherein the inherent viscosity of the polyester is from 0.65            to 0.75 dL/g as determined in 60/40 (wt/wt)            phenol/tetrachloroethane at a concentration of 0.25 g/50 ml            at 25° C.; and wherein the polyester has a Tg of 100 to 115°            C.

In one aspect, the invention relates to a polyester compositioncomprising at least one polyester which comprises:

-   -   (a) a dicarboxylic acid component comprising:        -   i) 70 to 100 mole % of terephthalic acid residues;        -   ii) 0 to 30 mole % of aromatic dicarboxylic acid residues            having up to 20 carbon atoms; and        -   iii) 0 to 10 mole % of aliphatic dicarboxylic acid residues            having up to 16 carbon atoms; and    -   (b) a glycol component comprising:        -   i) 5 to less than 50 mole % of            2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and        -   ii) greater than 50 to 95 mole % of cyclohexanedimethanol            residues,            wherein the total mole % of the dicarboxylic acid component            is 100 mole %, and the total mole % of the glycol component            is 100 mole %; and            wherein the inherent viscosity of the polyester is from 0.50            to 0.75 dL/g as determined in 60/40 (wt/wt)            phenol/tetrachloroethane at a concentration of 0.25 g/50 ml            at 25° C.; and wherein the polyester has a Tg of 95 to 115°            C.

In one aspect, the invention relates to a polyester compositioncomprising at least one polyester which comprises:

-   -   (a) a dicarboxylic acid component comprising:        -   i) 70 to 100 mole % of terephthalic acid residues;        -   ii) 0 to 30 mole % of aromatic dicarboxylic acid residues            having up to 20 carbon atoms; and        -   iii) 0 to 10 mole % of aliphatic dicarboxylic acid residues            having up to 16 carbon atoms; and    -   (b) a glycol component comprising:        -   i) 5 to less than 50 mole % of            2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and        -   ii) greater than 50 to 95 mole % of cyclohexanedimethanol            residues,            wherein the total mole % of the dicarboxylic acid component            is 100 mole %, and the total mole % of the glycol component            is 100 mole %; and            wherein the inherent viscosity of the polyester is from 0.50            to less than 0.75 dL/g as determined in 60/40 (wt/wt)            phenol/tetrachloroethane at a concentration of 0.25 g/50 ml            at 25° C.; and wherein the polyester has a Tg of 95 to 115°            C.

In one aspect, this invention relates to a polyester compositioncomprising at least one polyester which comprises:

-   -   (a) a dicarboxylic acid component comprising:        -   i) 70 to 100 mole % of terephthalic acid residues;        -   ii) 0 to 30 mole % of aromatic dicarboxylic acid residues            having up to 20 carbon atoms; and        -   iii) 0 to 10 mole % of aliphatic dicarboxylic acid residues            having up to 16 carbon atoms; and    -   (b) a glycol component comprising:        -   i) 10 to 30 mole % of            2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and        -   ii) 70 to 90 mole % of cyclohexanedimethanol residues,            wherein the total mole % of the dicarboxylic acid component            is 100 mole %, and the total mole % of the glycol component            is 100 mole %; and            wherein the inherent viscosity of the polyester is from 0.50            to 0.75 dL/g as determined in 60/40 (wt/wt)            phenol/tetrachloroethane at a concentration of 0.25 g/50 ml            at 25° C.; and wherein the polyester has a Tg of 95 to 115°            C.

In one aspect, this invention relates to a polyester compositioncomprising at least one polyester which comprises:

-   -   (a) a dicarboxylic acid component comprising:        -   i) 70 to 100 mole % of terephthalic acid residues;        -   ii) 0 to 30 mole % of aromatic dicarboxylic acid residues            having up to 20 carbon atoms; and        -   iii) 0 to 10 mole % of aliphatic dicarboxylic acid residues            having up to 16 carbon atoms; and    -   (b) a glycol component comprising:        -   i) 10 to 30 mole % of            2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and        -   ii) 70 to 90 mole % of cyclohexanedimethanol residues,            wherein the total mole % of the dicarboxylic acid component            is 100 mole %, and the total mole % of the glycol component            is 100 mole %; and            wherein the inherent viscosity of the polyester is from 0.50            to less than 0.75 dL/g as determined in 60/40 (wt/wt)            phenol/tetrachloroethane at a concentration of 0.25 g/50 ml            at 25° C.; and wherein the polyester has a Tg of 95 to 115°            C.

In one aspect, this invention relates to a polyester compositioncomprising at least one polyester which comprises:

-   -   (a) a dicarboxylic acid component comprising:        -   i) 70 to 100 mole % of terephthalic acid residues;        -   ii) 0 to 30 mole % of aromatic dicarboxylic acid residues            having up to 20 carbon atoms; and        -   iii) 0 to 10 mole % of aliphatic dicarboxylic acid residues            having up to 16 carbon atoms; and    -   (b) a glycol component comprising:        -   i) 15 to 25 mole % of            2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and        -   ii) 75 to 85 mole % of cyclohexanedimethanol residues,            wherein the total mole % of the dicarboxylic acid component            is 100 mole %, and the total mole % of the glycol component            is 100 mole %; and            wherein the inherent viscosity of the polyester is from 0.50            to 0.75 dL/g as determined in 60/40 (wt/wt)            phenol/tetrachloroethane at a concentration of 0.25 g/50 ml            at 25° C.; and wherein the polyester has a Tg of 95 to 115°            C.

In one aspect, this invention relates to a polyester compositioncomprising at least one polyester which comprises:

-   -   (a) a dicarboxylic acid component comprising:        -   i) 70 to 100 mole % of terephthalic acid residues;        -   ii) 0 to 30 mole % of aromatic dicarboxylic acid residues            having up to 20 carbon atoms; and        -   iii) 0 to 10 mole % of aliphatic dicarboxylic acid residues            having up to 16 carbon atoms; and    -   (b) a glycol component comprising:        -   i) 15 to 25 mole % of            2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and        -   ii) 75 to 85 mole % of cyclohexanedimethanol residues,            wherein the total mole % of the dicarboxylic acid component            is 100 mole %, and the total mole % of the glycol component            is 100 mole %; and            wherein the inherent viscosity of the polyester is from 0.50            to less than 0.75 dL/g as determined in 60/40 (wt/wt)            phenol/tetrachloroethane at a concentration of 0.25 g/50 ml            at 25° C.; and wherein the polyester has a Tg of 95 to 115°            C.

In one aspect, the invention relates to a polyester compositioncomprising at least one polyester which comprises:

-   -   (a) a dicarboxylic acid component comprising:        -   i) 70 to 100 mole % of terephthalic acid residues;        -   ii) 0 to 30 mole % of aromatic dicarboxylic acid residues            having up to 20 carbon atoms; and        -   iii) 0 to 10 mole % of aliphatic dicarboxylic acid residues            having up to 16 carbon atoms; and    -   (b) a glycol component comprising:        -   i) 15 to 25 mole % of            2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and        -   ii) 75 to 85 mole % of cyclohexanedimethanol residues,            wherein the total mole % of the dicarboxylic acid component            is 100 mole %, and the total mole % of the glycol component            is 100 mole %; and            wherein the inherent viscosity of the polyester is from 0.60            to 0.72 dL/g as determined in 60/40 (wt/wt)            phenol/tetrachloroethane at a concentration of 0.25 g/50 ml            at 25° C.; and wherein the polyester has a Tg of 95 to 115°            C.

In one aspect, the invention relates to a polyester compositioncomprising at least one polyester which comprises:

-   -   (a) a dicarboxylic acid component comprising:        -   i) 70 to 100 mole % of terephthalic acid residues;        -   ii) 0 to 30 mole % of aromatic dicarboxylic acid residues            having up to 20 carbon atoms; and        -   iii) 0 to 10 mole % of aliphatic dicarboxylic acid residues            having up to 16 carbon atoms; and    -   (b) a glycol component comprising:        -   i) 1 to 99 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol            residues; and        -   ii) 1 to 98.99 mole % of cyclohexanedimethanol            residues, iii) 0.01 to less than 15 mole % ethylene glycol;            wherein the total mole % of the dicarboxylic acid component            is 100 mole %, and the total mole % of the glycol component            is 100 mole %; and            wherein the inherent viscosity is 0.35 to 1.2 dL/g as            determined in 60/40 (wt/wt) phenol/tetrachloroethane at a            concentration of 0.25 g/50 ml at 25° C.; and            wherein the polyester has a Tg of 85 to 120° C.

In one aspect, the invention relates to a polyester compositioncomprising at least one polyester which comprises:

-   -   (a) a dicarboxylic acid component comprising:        -   i) 70 to 100 mole % of terephthalic acid residues;        -   ii) 0 to 30 mole % of aromatic dicarboxylic acid residues            having up to 20 carbon atoms; and        -   iii) 0 to 10 mole % of aliphatic dicarboxylic acid residues            having up to 16 carbon atoms; and    -   (b) a glycol component comprising:        -   i) 1 to 99 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol            residues; and        -   ii) 1 to 99 mole % of cyclohexanedimethanol residues,            wherein the total mole % of the dicarboxylic acid component            is 100 mole %, and the total mole % of the glycol component            is 100 mole %; and            wherein the inherent viscosity is 0.35 to 1.2 dL/g as            determined in 60/40 (wt/wt) phenol/tetrachloroethane at a            concentration of 0.25 g/50 ml at 25° C.; and            wherein the polyester has a Tg of 85 to 120° C.; and            optionally, wherein one or more branching agents is added            prior to or during the polymerization of the polyester.

In one aspect, the invention relates to a polyester compositioncomprising at least one polyester which comprises:

-   -   (a) a dicarboxylic acid component comprising:        -   i) 70 to 100 mole % of terephthalic acid residues;        -   ii) 0 to 30 mole % of aromatic dicarboxylic acid residues            having up to 20 carbon atoms; and        -   iii) 0 to 10 mole % of aliphatic dicarboxylic acid residues            having up to 16 carbon atoms;    -   (b) a glycol component comprising:        -   i) 1 to 99 mole % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol            residues; and        -   ii) 1 to 99 mole % of cyclohexanedimethanol residues; and    -   (c) residues from at least one branching agent;        wherein the total mole % of the dicarboxylic acid component is        100 mole %, and the total mole % of the glycol component is 100        mole %; and        wherein the inherent viscosity is 0.35 to 1.2 dL/g as determined        in 60/40 (wt/wt) phenol/tetrachloroethane at a concentration of        0.25 g/50 ml at 25° C.; and        wherein the polyester has a Tg of 85 to 120° C.

In one aspect, this invention relates to a polyester compositioncomprising:

-   -   at least one polyester which comprises:        -   (a) a dicarboxylic acid component comprising:            -   i) 70 to 100 mole % of terephthalic acid residues;            -   ii) 0 to 30 mole % of aromatic dicarboxylic acid                residues having up to 20 carbon atoms; and            -   iii) 0 to 10 mole % of aliphatic dicarboxylic acid                residues having up to 16 carbon atoms; and        -   (b) a glycol component comprising:            -   i) 1 to 99 mole % of 2,2,4,4-tetra                methyl-1,3-cyclobutanediol residues; and            -   ii) 1 to 99 mole % of cyclohexanedimethanol residues;                and    -   at least one thermal stabilizer or reaction products thereof;        wherein the total mole % of the dicarboxylic acid component is        100 mole %, and the total mole % of the glycol component is 100        mole %; and        wherein the inherent viscosity of the polyester is 0.35 to 1.2        dL/g as determined in 60/40 (wt/wt) phenol/tetrachloroethane at        a concentration of 0.25 g/50 ml at 25° C.; and wherein the        polyester has a Tg of 85 to 120° C.

In one aspect, the invention comprises a process for making any of thepolyesters useful in the invention comprising the following steps:

-   -   (I) heating a mixture at least one temperature chosen from        150° C. to 200° C., under at least one pressure chosen from the        range of 0 psig to 75 psig wherein said mixture comprises:        -   (a) a dicarboxylic acid component comprising:            -   (i) 70 to 100 mole % of terephthalic acid residues;            -   (ii) 0 to 30 mole % of aromatic dicarboxylic acid                residues having up to 20 carbon atoms; and            -   (iii) 0 to 10 mole % of aliphatic dicarboxylic acid                residues having up to 16 carbon atoms; and        -   (b) a glycol component comprising:            -   (i) 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues;                and            -   (ii) cyclohexanedimethanol residues;        -   wherein the molar ratio of glycol component/dicarboxylic            acid component added in Step (I) is 1.0-1.5/1.0;        -   wherein the mixture in Step (I) is heated in the presence            of:        -   (i) at least one catalyst comprising at least one tin            compound, and, optionally, at least one catalyst chosen from            titanium, gallium, zinc, antimony, cobalt, manganese,            magnesium, germanium, lithium, aluminum compounds and an            aluminum compound with lithium hydroxide or sodium            hydroxide; and (ii) at least one thermal stabilizer chosen            from at least one phosphorus compound, reaction products            thereof, and mixtures thereof;    -   (II) heating the product of Step (I) at a temperature of 230° C.        to 320° C. for 1 to 6 hours, under at least one pressure chosen        from the range of the final pressure of Step (I) to 0.02 torr        absolute, to form a final polyester;        wherein the total mole % of the dicarboxylic acid component of        the final polyester is 100 mole %; wherein the total mole % of        the glycol component of the final polyester is 100 mole %;        wherein the inherent viscosity of the final polyester is from        0.35 to 1.2 dL/g as determined in 60/40 (wt/wt)        phenol/tetrachloroethane at a concentration of 0.25 g/50 ml at        25° C.; and wherein the final polyester has a Tg of from 85 to        200° C.

In one aspect, the invention comprises a process for making any of thepolyesters of the invention comprising the following steps:

-   -   (I) heating a mixture at least one temperature chosen from        150° C. to 200° C., under at least one pressure chosen from the        range of 0 psig to 75 psig wherein said mixture comprises:        -   (a) a dicarboxylic acid component comprising:            -   (i) 70 to 100 mole % of terephthalic acid residues;            -   (ii) 0 to 30 mole % of aromatic dicarboxylic acid                residues having up to 20 carbon atoms; and            -   (iii) 0 to 10 mole % of aliphatic dicarboxylic acid                residues having up to 16 carbon atoms; and        -   (b) a glycol component comprising:            -   (i) 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues;                and            -   (ii) cyclohexanedimethanol residues;    -   wherein the molar ratio of glycol component/dicarboxylic acid        component added in Step (I) is 1.05-1.15/1.0;    -   wherein the mixture in Step (I) is heated in the presence        of: (i) at least one catalyst comprising at least one tin        compound, and, optionally, at least one catalyst chosen from        titanium, gallium, zinc, antimony, cobalt, manganese, magnesium,        germanium, lithium, aluminum compounds and an aluminum compound        with lithium hydroxide or sodium hydroxide; and (ii) at least        one thermal stabilizer chosen from at least one phosphorus        compound, reaction products thereof, and mixtures thereof;    -   (II) heating the product of Step (I) at a temperature of 230° C.        to 320° C. for 1 to 6 hours, under at least one pressure chosen        from the range of the final pressure of Step (I) to 0.02 torr        absolute, to form a final polyester;        wherein the total mole % of the dicarboxylic acid component of        the final polyester is 100 mole %; wherein the total mole % of        the glycol component of the final polyester is 100 mole %;        wherein the inherent viscosity of the final polyester is from        0.35 to 1.2 dL/g as determined in 60/40 (wt/wt)        phenol/tetrachloroethane at a concentration of 0.25 g/50 ml at        25° C.; and wherein the final polyester has a Tg of from 85 to        200° C.

In one aspect, the invention comprises a process for making any of thepolyesters of the invention comprising the following steps:

-   -   (I) heating a mixture at least one temperature chosen from        150° C. to 200° C., under at least one pressure chosen from the        range of 0 psig to 75 psig wherein said mixture comprises:        -   (a) a dicarboxylic acid component comprising:            -   (i) 70 to 100 mole % of terephthalic acid residues;            -   (ii) 0 to 30 mole % of aromatic dicarboxylic acid                residues having up to 20 carbon atoms; and            -   (iii) 0 to 10 mole % of aliphatic dicarboxylic acid                residues having up to 16 carbon atoms; and        -   (b) a glycol component comprising:            -   (i) 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues;                and            -   (ii) cyclohexanedimethanol residues;        -   wherein the molar ratio of glycol component/dicarboxylic            acid component added in Step (I) is 1.0-1.5/1.0;        -   wherein the mixture in Step (I) is heated in the presence            of: (i) at least one catalyst comprising at least one tin            compound, and, optionally, at least one catalyst chosen from            titanium, gallium, zinc, antimony, cobalt, manganese,            magnesium, germanium, lithium, aluminum compounds and an            aluminum compound with lithium hydroxide or sodium            hydroxide;    -   (II) heating the product of Step (I) at a temperature of 230° C.        to 320° C. for 1 to 6 hours under at least one pressure chosen        from the range of the final pressure of Step (I) to 0.02 torr        absolute, in the presence of at least one thermal stabilizer        chosen from at least one phosphorus compound, reaction products        thereof, and mixtures thereof;        wherein the total mole % of the dicarboxylic acid component of        the final polyester is 100 mole %; wherein the total mole % of        the glycol component of the final polyester is 100 mole %;        wherein the inherent viscosity of a final polyester is from 0.35        to 1.2 dL/g as determined in 60140 (wt/wt)        phenol/tetrachloroethane at a concentration of 0.25 g/50 ml at        25° C.; and wherein the final polyester has a Tg of from 85 to        200° C.

In one aspect, the invention comprises a process for making any of thepolyesters of the invention comprising the following steps:

-   -   (I) heating a mixture at least one temperature chosen from        150° C. to 200° C., under at least one pressure chosen from the        range of 0 psig to 75 psig wherein said mixture comprises:        -   (a) a dicarboxylic acid component comprising:            -   (i) 70 to 100 mole % of terephthalic acid residues;            -   (ii) 0 to 30 mole % of aromatic dicarboxylic acid                residues having up to 20 carbon atoms; and            -   (iii) 0 to 10 mole % of aliphatic dicarboxylic acid                residues having up to 16 carbon atoms; and        -   (b) a glycol component comprising:            -   (i) 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues;                and            -   (ii) cyclohexanedimethanol residues;        -   wherein the molar ratio of glycol component/dicarboxylic            acid component added in Step (I) is 1.05-1.15/1.0;        -   wherein the mixture in Step (I) is heated in the presence of            at least one catalyst comprising at least one tin compound,            and, optionally, at least one catalyst chosen from titanium,            gallium, zinc, antimony, cobalt, manganese, magnesium,            germanium, lithium, aluminum compounds and an aluminum            compound with lithium hydroxide or sodium hydroxide;    -   (II) heating the product of Step (I) at a temperature of 230° C.        to 320° C. for 1 to 6 hours under at least one pressure chosen        from the range of the final pressure of Step (I) to 0.02 torr        absolute, in the presence of at least one thermal stabilizer        chosen from at least one phosphorus compound, reaction products        thereof, and mixtures thereof;        wherein the total mole % of the dicarboxylic acid component of        the final polyester is 100 mole %; wherein the total mole % of        the glycol component of the final polyester is 100 mole %;        wherein the inherent viscosity of the final polyester is from        0.35 to 1.2 dL/g as determined in 60/40 (wt/wt)        phenol/tetrachloroethane at a concentration of 0.25 g/50 ml at        25° C.; and wherein the final polyester has a Tg of from 85 to        200° C.

In one aspect, the invention comprises a process for making any of thepolyesters of the invention comprising the following steps:

-   -   (I) heating a mixture at least one temperature chosen from        150° C. to 200° C., under at least one pressure chosen from the        range of 0 psig to 75 psig wherein said mixture comprises:        -   (a) a dicarboxylic acid component comprising:            -   (i) 70 to 100 mole % of terephthalic acid residues;            -   (ii) 0 to 30 mole % of aromatic dicarboxylic acid                residues having up to 20 carbon atoms; and            -   (iii) 0 to 10 mole % of aliphatic dicarboxylic acid                residues having up to 16 carbon atoms; and        -   (b) a glycol component comprising:            -   (i) 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues;                and            -   (ii) cyclohexanedimethanol residues;        -   wherein the molar ratio of glycol component/dicarboxylic            acid component added in Step (I) is 1.0-1.5/1.0;        -   wherein the mixture in Step (I) is heated in the presence            of:        -   (i) at least one catalyst comprising at least one tin            compound, and, optionally, at least one catalyst chosen from            titanium, gallium, zinc, antimony, cobalt, manganese,            magnesium, germanium, lithium, aluminum compounds and an            aluminum compound with lithium hydroxide or sodium            hydroxide; and (ii) at least one thermal stabilizer chosen            from at least one phosphorus compound, reaction products            thereof, and mixtures thereof;    -   (II) heating the product of Step (I) at a temperature of 250° C.        to 305° C. for 1 to 6 hours, under at least one pressure chosen        from the range of the final pressure of Step (I) to 0.02 torr        absolute, to form a final polyester;        wherein the total mole % of the dicarboxylic acid component of        the final polyester is 100 mole %; wherein the total mole % of        the glycol component of the final polyester is 100 mole %;        wherein the inherent viscosity of the final polyester is from        0.35 to 1.2 dL/g as determined in 60/40 (wt/wt)        phenol/tetrachloroethane at a concentration of 0.25 g/50 ml at        25° C.; and wherein the final polyester has a Tg of from 85 to        200° C.

In one aspect, the invention comprises a process for making any of thepolyesters of the invention comprising the following steps:

-   -   (I) heating a mixture at least one temperature chosen from        150° C. to 200° C., under at least one pressure chosen from the        range of 0 psig to 75 psig wherein said mixture comprises:        -   (a) a dicarboxylic acid component comprising:            -   (i) 70 to 100 mole % of terephthalic acid residues;            -   (ii) 0 to 30 mole % of aromatic dicarboxylic acid                residues having up to 20 carbon atoms; and            -   (iii) 0 to 10 mole % of aliphatic dicarboxylic acid                residues having up to 16 carbon atoms; and        -   (b) a glycol component comprising:            -   (i) 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues;                and            -   (ii) cyclohexanedimethanol residues;        -   wherein the molar ratio of glycol component/dicarboxylic            acid component added in Step (I) is 1.05-1.15/1.0;        -   wherein the mixture in Step (I) is heated in the presence            of:        -   (i) at least one catalyst comprising at least one tin            compound, and, optionally, at least one catalyst chosen from            titanium, gallium, zinc, antimony, cobalt, manganese,            magnesium, germanium, lithium, aluminum compounds and an            aluminum compound with lithium hydroxide or sodium            hydroxide; and (ii) at least one thermal stabilizer chosen            from at least one phosphorus compound, reaction products            thereof, and mixtures thereof;    -   (II) heating the product of Step (I) at a temperature of 250° C.        to 305° C. for 1 to 6 hours, under at least one pressure chosen        from the range of the final pressure of Step (I) to 0.02 torr        absolute, to form a final polyester;        wherein the total mole % of the dicarboxylic acid component of        the final polyester is 100 mole %; wherein the total mole % of        the glycol component of the final polyester is 100 mole %;        wherein the inherent viscosity of the final polyester is from        0.35 to 1.2 dL/g as determined in 60/40 (wt/wt)        phenol/tetrachloroethane at a concentration of 0.25 g/50 ml at        25° C.; and wherein the final polyester has a Tg of from 85 to        200° C.

In one aspect, the invention comprises a process for making any of thepolyesters of the invention comprising the following steps:

-   -   (I) heating a mixture at least one temperature chosen from        150° C. to 200° C., under at least one pressure chosen from the        range of 0 psig to 75 psig wherein said mixture comprises:        -   (a) a dicarboxylic acid component comprising:            -   (i) 70 to 100 mole % of terephthalic acid residues;            -   (ii) 0 to 30 mole % of aromatic dicarboxylic acid                residues having up to 20 carbon atoms; and            -   (iii) 0 to 10 mole % of aliphatic dicarboxylic acid                residues having up to 16 carbon atoms; and        -   (b) a glycol component comprising:            -   (i) 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues;                and            -   (ii) cyclohexanedimethanol residues;        -   wherein the molar ratio of glycol component/dicarboxylic            acid component added in Step (I) is 1.0-1.5/1.0;        -   wherein the mixture in Step (I) is heated in the presence of            at least one catalyst comprising at least one tin compound,            and, optionally, at least one catalyst chosen from titanium,            gallium, zinc, antimony, cobalt, manganese, magnesium,            germanium, lithium, aluminum compounds and an aluminum            compound with lithium hydroxide or sodium hydroxide;    -   (II) heating the product of Step (I) at a temperature of 250° C.        to 305° C. for 1 to 6 hours under at least one pressure chosen        from the range of the final pressure of Step (I) to 0.02 torr        absolute, in the presence of at least one thermal stabilizer        chosen from at least one phosphorus compound, reaction products        thereof, and mixtures thereof;        wherein the total mole % of the dicarboxylic acid component of        the final polyester is 100 mole %; wherein the total mole % of        the glycol component of the final polyester is 100 mole %;        wherein the inherent viscosity of the final polyester is from        0.35 to 1.2 dL/g as determined in 60/40 (wt/wt)        phenol/tetrachloroethane at a concentration of 0.25 g/50 ml at        25° C.; and wherein the final polyester has a Tg of from 85 to        200° C.

In one aspect, the invention comprises a process for making any of thepolyesters of the invention comprising the following steps:

-   -   (I) heating a mixture at least one temperature chosen from        150° C. to 200° C., under at least one pressure chosen from the        range of 0 psig to 75 psig wherein said mixture comprises:        -   (a) a dicarboxylic acid component comprising:            -   (i) 70 to 100 mole % of terephthalic acid residues;            -   (ii) 0 to 30 mole % of aromatic dicarboxylic acid                residues having up to 20 carbon atoms; and            -   (iii) 0 to 10 mole % of aliphatic dicarboxylic acid                residues having up to 16 carbon atoms; and        -   (b) a glycol component comprising:            -   (i) 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues;                and            -   (ii) cyclohexanedimethanol residues;        -   wherein the molar ratio of glycol component/dicarboxylic            acid component added in Step (I) is 1.05-1.15/1.0;        -   wherein the mixture in Step (I) is heated in the presence of            at least one catalyst comprising at least one tin compound,            and, optionally, at least one catalyst chosen from titanium,            gallium, zinc, antimony, cobalt, manganese, magnesium,            germanium, lithium, aluminum compounds and an aluminum            compound with lithium hydroxide or sodium hydroxide;    -   (II) heating the product of Step (I) at a temperature of 250° C.        to 305° C. for 1 to 6 hours under at least one pressure chosen        from the range of the final pressure of Step (I) to 0.02 torr        absolute, in the presence of at least one thermal stabilizer        chosen from at least one phosphorus compound, reaction products        thereof, and mixtures thereof;        wherein the total mole % of the dicarboxylic acid component of        the final polyester is 100 mole %; wherein the total mole % of        the glycol component of the final polyester is 100 mole %;        wherein the inherent viscosity of the final polyester is from        0.35 to 1.2 dL/g as determined in 60/40 (wt/wt)        phenol/tetrachloroethane at a concentration of 0.25 g/50 ml at        25° C.; and wherein the final polyester has a Tg of from 85 to        200° C.

In one aspect, the invention comprises a process for making any of thepolyesters of the invention comprising the following steps:

-   -   (I) heating a mixture at least one temperature chosen from        150° C. to 200° C., under at least one pressure chosen from the        range of 0 psig to 75 psig wherein said mixture comprises:        -   (a) a dicarboxylic acid component comprising:            -   (i) 70 to 100 mole % of terephthalic acid residues;            -   (ii) 0 to 30 mole % of aromatic dicarboxylic acid                residues having up to 20 carbon atoms; and            -   (iii) 0 to 10 mole % of aliphatic dicarboxylic acid                residues having up to 16 carbon atoms; and        -   (b) a glycol component comprising:            -   (i) 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues;                and            -   (ii) cyclohexanedimethanol residues;        -   wherein the molar ratio of glycol component/dicarboxylic            acid component added in Step (I) is 1.0-1.5/1.0;        -   wherein the mixture in Step (I) is heated in the presence            of: (i) at least one catalyst comprising at least one tin            compound, and, optionally, at least one catalyst chosen from            titanium, gallium, zinc, antimony, cobalt, manganese,            magnesium, germanium, lithium, aluminum compounds and an            aluminum compound with lithium hydroxide or sodium            hydroxide; and (ii) at least one thermal stabilizer chosen            from at least one of alkyl phosphate esters, aryl phosphate            esters, mixed alkyl aryl phosphate esters, reaction products            thereof, and mixtures thereof;    -   (II) heating the product of Step (I) at a temperature of 230° C.        to 320° C. for 1 to 6 hours, under at least one pressure chosen        from the range of the final pressure of Step (I) to 0.02 torr        absolute, to form a final polyester;        wherein the total mole % of the dicarboxylic acid component of        the final polyester is 100 mole %; wherein the total mole % of        the glycol component of the final polyester is 100 mole %;        wherein the inherent viscosity of the final polyester is from        0.35 to 1.2 dL/g as determined in 60/40 (wt/wt)        phenol/tetrachloroethane at a concentration of 0.25 g/50 ml at        25° C.; and wherein the final polyester has a Tg of from 85 to        200° C.

In one aspect, the invention comprises a process for making any of thepolyesters useful in the invention comprising the following steps:

-   -   (I) heating a mixture at least one temperature chosen from        150° C. to 200° C., under at least one pressure chosen from the        range of 0 psig to 75 psig wherein said mixture comprises:        -   (a) a dicarboxylic acid component comprising:            -   (i) 70 to 100 mole % of terephthalic acid residues;            -   (ii) 0 to 30 mole % of aromatic dicarboxylic acid                residues having up to 20 carbon atoms; and            -   (iii) 0 to 10 mole % of aliphatic dicarboxylic acid                residues having up to 16 carbon atoms; and        -   (b) a glycol component comprising:            -   (i) 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues;                and            -   (ii) cyclohexanedimethanol residues;        -   wherein the molar ratio of glycol component/dicarboxylic            acid component added in Step (I) is 1.05-1.15/1.0;        -   wherein the mixture in Step (I) is heated in the presence            of:        -   (i) at least one catalyst comprising at least one tin            compound, and, optionally, at least one catalyst chosen from            titanium, gallium, zinc, antimony, cobalt, manganese,            magnesium, germanium, lithium, aluminum compounds and an            aluminum compound with lithium hydroxide or sodium            hydroxide; and (ii) at least one thermal stabilizer chosen            from at least one of alkyl phosphate esters, aryl phosphate            esters, mixed alkyl aryl phosphate esters, reaction products            thereof, and mixtures thereof; to form a polyester; and    -   (II) heating the product of Step (I) at a temperature of 230° C.        to 320° C. for 1 to 6 hours, under at least one pressure chosen        from the range of the final pressure of Step (I) to 0.02 torr        absolute, to form a final polyester;        wherein the total mole % of the dicarboxylic acid component of        the final polyester is 100 mole %; wherein the total mole % of        the glycol component of the final polyester is 100 mole %;        wherein the inherent viscosity of the final polyester is from        0.35 to 1.2 dL/g as determined in 60/40 (wt/wt)        phenol/tetrachloroethane at a concentration of 0.25 g/50 ml at        25° C.; and wherein the final polyester has a Tg of from 85 to        200° C.

In one aspect, the invention comprises a process for making any of thepolyesters useful in the invention comprising the following steps:

-   -   (I) heating a mixture at least one temperature chosen from        150° C. to 200° C., under at least one pressure chosen from the        range of 0 psig to 75 psig wherein said mixture comprises:        -   (a) a dicarboxylic acid component comprising:            -   (i) 70 to 100 mole % of terephthalic acid residues;            -   (ii) 0 to 30 mole % of aromatic dicarboxylic acid                residues having up to 20 carbon atoms; and            -   (iii) 0 to 10 mole % of aliphatic dicarboxylic acid                residues having up to 16 carbon atoms; and        -   (b) a glycol component comprising:            -   (i) 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues;                and            -   (ii) cyclohexanedimethanol residues;        -   wherein the molar ratio of glycol component/dicarboxylic            acid component added in Step (I) is 1.0-1.5/1.0;        -   wherein the mixture in Step (I) is heated in the presence of            at least one catalyst comprising at least one tin compound,            and, optionally, at least one catalyst chosen from titanium,            gallium, zinc, antimony, cobalt, manganese, magnesium,            germanium, lithium, aluminum compounds and an aluminum            compound with lithium hydroxide or sodium hydroxide;    -   (II) heating the product of Step (I) at a temperature of 230° C.        to 320° C. for 1 to 6 hours under at least one pressure chosen        from the range of the final pressure of Step (I) to 0.02 torr        absolute, in the presence of at least one thermal stabilizer        chosen from at least one of alkyl phosphate esters, aryl        phosphate esters, mixed alkyl aryl phosphate esters, reaction        products thereof, and mixtures thereof; to form a polyester; and        wherein the total mole % of the dicarboxylic acid component of        the final polyester is 100 mole %; wherein the total mole % of        the glycol component of the final polyester is 100 mole %;        wherein the inherent viscosity of the final polyester is from        0.35 to 1.2 dL/g as determined in 60/40 (wt/wt)        phenol/tetrachloroethane at a concentration of 0.25 g/50 ml at        25° C.; and wherein the final polyester has a Tg of from 85 to        200° C.

In one aspect, the invention comprises a process for making any of thepolyesters useful in the invention comprising the following steps:

-   -   (I) heating a mixture at least one temperature chosen from        150° C. to 200° C., under at least one pressure chosen from the        range of 0 psig to 75 psig wherein said mixture comprises:        -   (a) a dicarboxylic acid component comprising:            -   (i) 70 to 100 mole % of terephthalic acid residues;            -   (ii) 0 to 30 mole % of aromatic dicarboxylic acid                residues having up to 20 carbon atoms; and            -   (iii) 0 to 10 mole % of aliphatic dicarboxylic acid                residues having up to 16 carbon atoms; and        -   (b) a glycol component comprising:            -   (i) 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues;                and            -   (ii) cyclohexanedimethanol residues;        -   wherein the molar ratio of glycol component/dicarboxylic            acid component added in Step (I) is 1.05-1.15/1.0;        -   wherein the mixture in Step (I) is heated in the presence of            at least one catalyst comprising at least one tin compound,            and, optionally, at least one catalyst chosen from titanium,            gallium, zinc, antimony, cobalt, manganese, magnesium,            germanium, lithium, aluminum compounds and an aluminum            compound with lithium hydroxide or sodium hydroxide;    -   (II) heating the product of Step (I) at a temperature of 230° C.        to 320° C. for 1 to 6 hours under at least one pressure chosen        from the range of the final pressure of Step (I) to 0.02 torr        absolute, in the presence of at least one thermal stabilizer        chosen from at least one of alkyl phosphate esters, aryl        phosphate esters, mixed alkyl aryl phosphate esters, reaction        products thereof, and mixtures thereof; to form a polyester;        wherein the total mole % of the dicarboxylic acid component of        the final polyester is 100 mole %; wherein the total mole % of        the glycol component of the final polyester is 100 mole %;        wherein the inherent viscosity of the final polyester is from        0.35 to 1.2 dL/g as determined in 60/40 (wt/wt)        phenol/tetrachloroethane at a concentration of 0.25 g/50 ml at        25° C.; and wherein the final polyester has a Tg of from 85 to        200° C.

In one aspect, the invention comprises a process for making any of thepolyesters useful in the invention comprising the following steps:

-   -   (I) heating a mixture at least one temperature chosen from        150° C. to 200° C., under at least one pressure chosen from the        range of 0 psig to 75 psig wherein said mixture comprises:        -   (a) a dicarboxylic acid component comprising:            -   (i) 70 to 100 mole % of terephthalic acid residues;            -   (ii) 0 to 30 mole % of aromatic dicarboxylic acid                residues having up to 20 carbon atoms; and            -   (iii) 0 to 10 mole % of aliphatic dicarboxylic acid                residues having up to 16 carbon atoms; and        -   (b) a glycol component comprising:            -   (i) 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues;                and            -   (ii) cyclohexanedimethanol residues;        -   wherein the molar ratio of glycol component/dicarboxylic            acid component added in Step (I) is 1.0-1.5/1.0;        -   wherein the mixture in Step (I) is heated in the presence            of:        -   (i) at least one catalyst comprising at least one tin            compound, and, optionally, at least one catalyst chosen from            titanium, gallium, zinc, antimony, cobalt, manganese,            magnesium, germanium, lithium, aluminum compounds and an            aluminum compound with lithium hydroxide or sodium            hydroxide; and (ii) at least one thermal stabilizer chosen            from at least one of alkyl phosphate esters, aryl phosphate            esters, mixed alkyl aryl phosphate esters, reaction products            thereof, and mixtures thereof;    -   (II) heating the product of Step (I) at a temperature of 230° C.        to 320° C. for 1 to 6 hours, under at least one pressure chosen        from the range of the final pressure of Step (I) to 0.02 torr        absolute, to form a final polyester;        wherein the total mole % of the dicarboxylic acid component of        the final polyester is 100 mole %; wherein the total mole % of        the glycol component of the final polyester is 100 mole %;        wherein the inherent viscosity of the final polyester is from        0.35 to 1.2 dL/g as determined in 60/40 (wt/wt)        phenol/tetrachloroethane at a concentration of 0.25 g/50 ml at        25° C.; and wherein the final polyester has a Tg of from 85 to        200° C.

In one aspect, the invention comprises a process for making any of thepolyesters useful in the invention comprising the following steps:

-   -   (I) heating a mixture at least one temperature chosen from        150° C. to 200° C., under at least one pressure chosen from the        range of 0 psig to 75 psig wherein said mixture comprises:        -   (a) a dicarboxylic acid component comprising:            -   (i) 70 to 100 mole % of terephthalic acid residues;            -   (ii) 0 to 30 mole % of aromatic dicarboxylic acid                residues having up to 20 carbon atoms; and            -   (iii) 0 to 10 mole % of aliphatic dicarboxylic acid                residues having up to 16 carbon atoms; and        -   (b) a glycol component comprising:            -   (i) 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues;                and            -   (ii) cyclohexanedimethanol residues;        -   wherein the molar ratio of glycol component/dicarboxylic            acid component added in Step (I) is 1.05-1.15/1.0;        -   wherein the mixture in Step (I) is heated in the presence            of: (i) at least one catalyst comprising at least one tin            compound, and, optionally, at least one titanium, gallium,            zinc, antimony, cobalt, manganese, magnesium, germanium,            lithium, aluminum compounds and an aluminum compound with            lithium hydroxide or sodium hydroxide; and (ii) at least one            thermal stabilizer chosen from at least one of alkyl            phosphate esters, aryl phosphate esters, mixed alkyl aryl            phosphate esters, reaction products thereof, and mixtures            thereof;    -   (II) heating the product of Step (I) at a temperature of 230° C.        to 320° C. for 1 to 6 hours, under at least one pressure chosen        from the range of the final pressure of Step (I) to 0.02 torr        absolute, to form a final polyester;        wherein the total mole % of the dicarboxylic acid component of        the final polyester is 100 mole %; wherein the total mole % of        the glycol component of the final polyester is 100 mole %;        wherein the inherent viscosity of the final polyester is from        0.35 to 1.2 dL/g as determined in 60/40 (wt/wt)        phenol/tetrachloroethane at a concentration of 0.25 g/50 ml at        25° C.; and wherein the final polyester has a Tg of from 85 to        200° C.

In one aspect, the invention comprises a process for making any of thepolyesters useful in the invention comprising the following steps:

-   -   (I) heating a mixture at least one temperature chosen from        150° C. to 200° C., under at least one pressure chosen from the        range of 0 psig to 75 psig wherein said mixture comprises:        -   (a) a dicarboxylic acid component comprising:            -   (i) 70 to 100 mole % of terephthalic acid residues;            -   (ii) 0 to 30 mole % of aromatic dicarboxylic acid                residues having up to 20 carbon atoms; and            -   (iii) 0 to 10 mole % of aliphatic dicarboxylic acid                residues having up to 16 carbon atoms; and        -   (b) a glycol component comprising:            -   (i) 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues;                and            -   (ii) cyclohexanedimethanol residues;        -   wherein the molar ratio of glycol component/dicarboxylic            acid component added in Step (I) is 1.0-1.5/1.0;        -   wherein the mixture in Step (I) is heated in the presence            of: (i) at least one catalyst comprising at least one tin            compound, and, optionally, at least one catalyst chosen from            titanium, gallium, zinc, antimony, cobalt, manganese,            magnesium, germanium, lithium, aluminum compounds and an            aluminum compound with lithium hydroxide or sodium            hydroxide;    -   (II) heating the product of Step (I) at a temperature of 230° C.        to 320° C. for 1 to 6 hours under at least one pressure chosen        from the range of the final pressure of Step (I) to 0.02 torr        absolute, in the presence of at least one thermal stabilizer        chosen from at least one of alkyl phosphate esters, aryl        phosphate esters, mixed alkyl aryl phosphate esters, reaction        products thereof, and mixtures thereof;        wherein the total mole % of the dicarboxylic acid component of        the final polyester is 100 mole %; wherein the total mole % of        the glycol component of the final polyester is 100 mole %;        wherein the inherent viscosity of a final polyester is from 0.35        to 1.2 dL/g as determined in 60/40 (wt/wt)        phenol/tetrachloroethane at a concentration of 0.25 g/50 ml at        25° C.; and wherein the final polyester has a Tg of from 85 to        200° C.

In one aspect, the invention comprises a process for making any of thepolyesters useful in the invention comprising the following steps:

-   -   (I) heating a mixture at least one temperature chosen from        150° C. to 200° C., under at least one pressure chosen from the        range of 0 psig to 75 psig wherein said mixture comprises:        -   (a) a dicarboxylic acid component comprising:            -   (i) 70 to 100 mole % of terephthalic acid residues;            -   (ii) 0 to 30 mole % of aromatic dicarboxylic acid                residues having up to 20 carbon atoms; and            -   (iii) 0 to 10 mole % of aliphatic dicarboxylic acid                residues having up to 16 carbon atoms; and        -   (b) a glycol component comprising:            -   (i) 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues;                and            -   (ii) cyclohexanedimethanol residues;        -   wherein the molar ratio of glycol component/dicarboxylic            acid component added in Step (I) is 1.05-1.15/1.0;        -   wherein the mixture in Step (I) is heated in the presence of            at least one catalyst comprising at least one tin compound,            and, optionally, at least one catalyst chosen from titanium,            gallium, zinc, antimony, cobalt, manganese, magnesium,            germanium, lithium, aluminum compounds and an aluminum            compound with lithium hydroxide or sodium hydroxide;    -   (II) heating the product of Step (I) at a temperature of 230° C.        to 320° C. for 1 to 6 hours under at least one pressure chosen        from the range of the final pressure of Step (I) to 0.02 torr        absolute, in the presence of at least one thermal stabilizer        chosen from at least one of alkyl phosphate esters, aryl        phosphate esters, mixed alkyl aryl phosphate esters, reaction        products thereof, and mixtures thereof;        wherein the total mole % of the dicarboxylic acid component of        the final polyester is 100 mole %; wherein the total mole % of        the glycol component of the final polyester is 100 mole %;        wherein the inherent viscosity of the final polyester is from        0.35 to 1.2 dL/g as determined in 60/40 (wt/wt)        phenol/tetrachloroethane at a concentration of 0.25 g/50 ml at        25° C.; and wherein the final polyester has a Tg of from 85 to        200° C.

In one aspect, the invention comprises a process for making any of thepolyesters useful in the invention comprising the following steps:

-   -   (I) heating a mixture at least one temperature chosen from        150° C. to 200° C., under at least one pressure chosen from the        range of 0 psig to 75 psig wherein said mixture comprises:        -   (a) a dicarboxylic acid component comprising:            -   (i) 70 to 100 mole % of terephthalic acid residues;            -   (ii) 0 to 30 mole % of aromatic dicarboxylic acid                residues having up to 20 carbon atoms; and            -   (iii) 0 to 10 mole % of aliphatic dicarboxylic acid                residues having up to 16 carbon atoms; and        -   (b) a glycol component comprising:            -   (i) 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues;                and            -   (ii) cyclohexanedimethanol residues;        -   wherein the molar ratio of glycol component/dicarboxylic            acid component added in Step (I) is 1.0-1.5/1.0;        -   wherein the mixture in Step (I) is heated in the presence            of:        -   (i) at least one catalyst comprising at least one tin            compound, and, optionally, at least one catalyst chosen from            titanium, gallium, zinc, antimony, cobalt, manganese,            magnesium, germanium, lithium, aluminum compounds and an            aluminum compound with lithium hydroxide or sodium            hydroxide; and (ii) at least one thermal stabilizer chosen            from at least one of alkyl phosphate esters, aryl phosphate            esters, mixed alkyl aryl phosphate esters, reaction products            thereof, and mixtures thereof;    -   (II) heating the product of Step (I) at a temperature of 250° C.        to 305° C. for 1 to 6 hours, under at least one pressure chosen        from the range of the final pressure of Step (I) to 0.02 torr        absolute, to form a final polyester;        wherein the total mole % of the dicarboxylic acid component of        the final polyester is 100 mole %; wherein the total mole % of        the glycol component of the final polyester is 100 mole %;        wherein the inherent viscosity of the final polyester is from        0.35 to 1.2 dL/g as determined in 60/40 (wt/wt)        phenol/tetrachloroethane at a concentration of 0.25 g/50 ml at        25° C.; and wherein the final polyester has a Tg of from 85 to        200° C.

In one aspect, the invention comprises a process for making any of thepolyesters useful in the invention comprising the following steps:

-   -   (I) heating a mixture at least one temperature chosen from        150° C. to 200° C., under at least one pressure chosen from the        range of 0 psig to 75 psig wherein said mixture comprises:        -   (a) a dicarboxylic acid component comprising:            -   (i) 70 to 100 mole % of terephthalic acid residues;            -   (ii) 0 to 30 mole % of aromatic dicarboxylic acid                residues having up to 20 carbon atoms; and            -   (iii) 0 to 10 mole % of aliphatic dicarboxylic acid                residues having up to 16 carbon atoms; and        -   (b) a glycol component comprising:            -   (i) 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues;                and            -   (ii) cyclohexanedimethanol residues;        -   wherein the molar ratio of glycol component/dicarboxylic            acid component added in Step (I) is 1.05-1.15/1.0;        -   wherein the mixture in Step (I) is heated in the presence            of:        -   (i) at least one catalyst comprising at least one tin            compound, and, optionally, at least one catalyst chosen from            titanium, gallium, zinc, antimony, cobalt, manganese,            magnesium, germanium, lithium, aluminum compounds and an            aluminum compound with lithium hydroxide or sodium            hydroxide; and (ii) at least one thermal stabilizer chosen            from at least one of alkyl phosphate esters, aryl phosphate            esters, mixed alkyl aryl phosphate esters, reaction products            thereof, and mixtures thereof;    -   (II) heating the product of Step (I) at a temperature of 250° C.        to 305° C. for 1 to 6 hours, under at least one pressure chosen        from the range of the final pressure of Step (I) to 0.02 torr        absolute, to form a final polyester;        wherein the total mole % of the dicarboxylic acid component of        the final polyester is 100 mole %; wherein the total mole % of        the glycol component of the final polyester is 100 mole %;        wherein the inherent viscosity of the final polyester is from        0.35 to 1.2 dL/g as determined in 60/40 (wt/wt)        phenol/tetrachloroethane at a concentration of 0.25 g/50 ml at        25° C.; and wherein the final polyester has a Tg of from 85 to        200° C.

In one aspect, the invention comprises a process for making any of thepolyesters useful in the invention comprising the following steps:

-   -   (I) heating a mixture at least one temperature chosen from        150° C. to 200° C., under at least one pressure chosen from the        range of 0 psig to 75 psig wherein said mixture comprises:        -   (a) a dicarboxylic acid component comprising:            -   (i) 70 to 100 mole % of terephthalic acid residues;            -   (ii) 0 to 30 mole % of aromatic dicarboxylic acid                residues having up to 20 carbon atoms; and            -   (iii) 0 to 10 mole % of aliphatic dicarboxylic acid                residues having up to 16 carbon atoms; and        -   (b) a glycol component comprising:            -   (i) 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues;                and            -   (ii) cyclohexanedimethanol residues;        -   wherein the molar ratio of glycol component/dicarboxylic            acid component added in Step (I) is 1.0-1.5/1.0;        -   wherein the mixture in Step (I) is heated in the presence of            at least one catalyst comprising at least one tin compound,            and, optionally, at least one catalyst chosen from titanium,            gallium, zinc, antimony, cobalt, manganese, magnesium,            germanium, lithium, aluminum compounds and an aluminum            compound with lithium hydroxide or sodium hydroxide;    -   (II) heating the product of Step (I) at a temperature of 250° C.        to 305° C. for 1 to 6 hours under at least one pressure chosen        from the range of the final pressure of Step (I) to 0.02 torr        absolute, in the presence of at least one thermal stabilizer        chosen from at least one of alkyl phosphate esters, aryl        phosphate esters, mixed alkyl aryl phosphate esters, reaction        products thereof, and mixtures thereof;        wherein the total mole % of the dicarboxylic acid component of        the final polyester is 100 mole %; wherein the total mole % of        the glycol component of the final polyester is 100 mole %;        wherein the inherent viscosity of the final polyester is from        0.35 to 1.2 dL/g as determined in 60/40 (wt/wt)        phenol/tetrachloroethane at a concentration of 0.25 g/50 ml at        25° C.; and wherein the final polyester has a Tg of from 85 to        200° C.

In one aspect, the invention comprises a process for making any of thepolyesters useful in the invention comprising the following steps:

-   -   (I) heating a mixture at least one temperature chosen from        150° C. to 200° C., under at least one pressure chosen from the        range of 0 psig to 75 psig wherein said mixture comprises:        -   (a) a dicarboxylic acid component comprising:            -   (i) 70 to 100 mole % of terephthalic acid residues;            -   (ii) 0 to 30 mole % of aromatic dicarboxylic acid                residues having up to 20 carbon atoms; and            -   (iii) 0 to 10 mole % of aliphatic dicarboxylic acid                residues having up to 16 carbon atoms; and        -   (b) a glycol component comprising:            -   (i) 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues;                and            -   (ii) cyclohexanedimethanol residues;        -   wherein the molar ratio of glycol component/dicarboxylic            acid component added in Step (I) is 1.05-1.15/1.0;        -   wherein the mixture in Step (I) is heated in the presence of            at least one catalyst comprising at least one tin compound,            and, optionally, at least one catalyst chosen from titanium,            gallium, zinc, antimony, cobalt, manganese, magnesium,            germanium, lithium, aluminum compounds and an aluminum            compound with lithium hydroxide or sodium hydroxide;    -   (II) heating the product of Step (I) at a temperature of 250° C.        to 305° C. for 1 to 6 hours under at least one pressure chosen        from the range of the final pressure of Step (I) to 0.02 torr        absolute, in the presence of at least one thermal stabilizer        chosen from at least one of alkyl phosphate esters, aryl        phosphate esters, mixed alkyl aryl phosphate esters, reaction        products thereof, and mixtures thereof;        wherein the total mole % of the dicarboxylic acid component of        the final polyester is 100 mole %; wherein the total mole % of        the glycol component of the final polyester is 100 mole %;        wherein the inherent viscosity of the final polyester is from        0.35 to 1.2 dL/g as determined in 60/40 (wt/wt)        phenol/tetrachloroethane at a concentration of 0.25 g/50 ml at        25° C.; and wherein the final polyester has a Tg of from 85 to        200° C.

In one aspect, the invention comprises a process for making any of thepolyesters useful in the invention comprising the following steps:

-   -   (I) heating a mixture at least one temperature chosen from        150° C. to 200° C., under at least one pressure chosen from the        range of 0 psig to 75 psig wherein said mixture comprises:        -   (a) a dicarboxylic acid component comprising:            -   (i) 70 to 100 mole % of terephthalic acid residues;            -   (ii) 0 to 30 mole % of aromatic dicarboxylic acid                residues having up to 20 carbon atoms; and            -   (iii) 0 to 10 mole % of aliphatic dicarboxylic acid                residues having up to 16 carbon atoms; and        -   (b) a glycol component comprising:            -   (i) 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues;                and            -   (ii) cyclohexanedimethanol residues;        -   wherein the molar ratio of glycol component/dicarboxylic            acid component added in Step (I) is 1.0-1.5/1.0;        -   wherein the mixture in Step (I) is heated in the presence            of: (i) at least one catalyst comprising at least one tin            compound, and, optionally, at least one catalyst chosen from            titanium, gallium, zinc, antimony, cobalt, manganese,            magnesium, germanium, lithium, aluminum compounds and an            aluminum compound with lithium hydroxide or sodium            hydroxide; and (ii) at least one thermal stabilizer chosen            from at least one of alkyl phosphate esters, aryl phosphate            esters, mixed alkyl aryl phosphate esters, reaction products            thereof, and mixtures thereof;    -   (II) heating the product of Step (I) at a temperature of 230° C.        to 320° C. for 1 to 6 hours, under at least one pressure chosen        from the range of the final pressure of Step (I) to 0.02 torr        absolute, to form a final polyester;        wherein the total mole % of the dicarboxylic acid component of        the final polyester is 100 mole %; wherein the total mole % of        the glycol component of the final polyester is 100 mole %;        wherein the inherent viscosity of the final polyester is from        0.35 to 1.2 dL/g as determined in 60/40 (wt/wt)        phenol/tetrachloroethane at a concentration of 0.25 g/50 ml at        25° C.; and wherein the final polyester has a Tg of from 85 to        200° C.

In one aspect, the invention comprises a process for making any of thepolyesters useful in the invention comprising the following steps:

-   -   (I) heating a mixture at least one temperature chosen from        150° C. to 200° C., under at least one pressure chosen from the        range of 0 psig to 75 psig wherein said mixture comprises:        -   (a) a dicarboxylic acid component comprising:            -   (i) 70 to 100 mole % of terephthalic acid residues;            -   (ii) 0 to 30 mole % of aromatic dicarboxylic acid                residues having up to 20 carbon atoms; and            -   (iii) 0 to 10 mole % of aliphatic dicarboxylic acid                residues having up to 16 carbon atoms; and        -   (b) a glycol component comprising:            -   (i) 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues;                and            -   (ii) cyclohexanedimethanol residues;        -   wherein the molar ratio of glycol component/dicarboxylic            acid component added in Step (I) is 1.05-1.15/1.0;        -   wherein the mixture in Step (I) is heated in the presence            of:        -   (i) at least one catalyst comprising at least one tin            compound, and, optionally, at least one catalyst chosen from            titanium, gallium, zinc, antimony, cobalt, manganese,            magnesium, germanium, lithium, aluminum compounds and an            aluminum compound with lithium hydroxide or sodium            hydroxide; and (ii) at least one thermal stabilizer chosen            from at least one of alkyl phosphate esters, aryl phosphate            esters, mixed alkyl aryl phosphate esters, reaction products            thereof, and mixtures thereof; to form a polyester; and    -   (II) heating the product of Step (I) at a temperature of 230° C.        to 320° C. for 1 to 6 hours, under at least one pressure chosen        from the range of the final pressure of Step (I) to 0.02 torr        absolute, to form a final polyester;        wherein the total mole % of the dicarboxylic acid component of        the final polyester is 100 mole %; wherein the total mole % of        the glycol component of the final polyester is 100 mole %;        wherein the inherent viscosity of the final polyester is from        0.35 to 1.2 dL/g as determined in 60/40 (wt/wt)        phenol/tetrachloroethane at a concentration of 0.25 g/50 ml at        25° C.; and wherein the final polyester has a Tg of from 85 to        200° C.

In one aspect, the invention comprises a process for making any of thepolyesters useful in the invention comprising the following steps:

-   -   (I) heating a mixture at least one temperature chosen from        150° C. to 200° C., under at least one pressure chosen from the        range of 0 psig to 75 psig wherein said mixture comprises:        -   (a) a dicarboxylic acid component comprising:            -   (i) 70 to 100 mole % of terephthalic acid residues;            -   (ii) 0 to 30 mole % of aromatic dicarboxylic acid                residues having up to 20 carbon atoms; and            -   (iii) 0 to 10 mole % of aliphatic dicarboxylic acid                residues having up to 16 carbon atoms; and        -   (b) a glycol component comprising:            -   (i) 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues;                and            -   (ii) cyclohexanedimethanol residues;        -   wherein the molar ratio of glycol component/dicarboxylic            acid component added in Step (I) is 1.0-1.5/1.0;        -   wherein the mixture in Step (I) is heated in the presence of            at least one catalyst comprising at least one tin compound,            and, optionally, at least one catalyst chosen from titanium,            gallium, zinc, antimony, cobalt, manganese, magnesium,            germanium, lithium, aluminum compounds and an aluminum            compound with lithium hydroxide or sodium hydroxide;    -   (II) heating the product of Step (I) at a temperature of 230° C.        to 320° C. for 1 to 6 hours under at least one pressure chosen        from the range of the final pressure of Step (I) to 0.02 torr        absolute, in the presence of at least one thermal stabilizer        chosen from at least one of alkyl phosphate esters, aryl        phosphate esters, mixed alkyl aryl phosphate esters, reaction        products thereof, and mixtures thereof; to form a polyester; and        wherein the total mole % of the dicarboxylic acid component of        the final polyester is 100 mole %; wherein the total mole % of        the glycol component of the final polyester is 100 mole %;        wherein the inherent viscosity of the final polyester is from        0.35 to 1.2 dL/g as determined in 60/40 (wt/wt)        phenol/tetrachloroethane at a concentration of 0.25 g/50 ml at        25° C.; and wherein the final polyester has a Tg of from 85 to        200° C.

In one aspect, the invention comprises a process for making any of thepolyesters useful in the invention comprising the following steps:

-   -   (I) heating a mixture at least one temperature chosen from        150° C. to 200° C., under at least one pressure chosen from the        range of 0 psig to 75 psig wherein said mixture comprises:        -   (a) a dicarboxylic acid component comprising:            -   (i) 70 to 100 mole % of terephthalic acid residues;            -   (ii) 0 to 30 mole % of aromatic dicarboxylic acid                residues having up to 20 carbon atoms; and            -   (iii) 0 to 10 mole % of aliphatic dicarboxylic acid                residues having up to 16 carbon atoms; and        -   (b) a glycol component comprising:            -   (i) 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues;                and            -   (ii) cyclohexanedimethanol residues;        -   wherein the molar ratio of glycol component/dicarboxylic            acid component added in Step (I) is 1.05-1.15/1.0;        -   wherein the mixture in Step (I) is heated in the presence of            at least one catalyst comprising at least one tin compound,            and, optionally, at least one catalyst chosen from titanium,            gallium, zinc, antimony, cobalt, manganese, magnesium,            germanium, lithium, aluminum compounds and an aluminum            compound with lithium hydroxide or sodium hydroxide;    -   (II) heating the product of Step (I) at a temperature of 230° C.        to 320° C. for 1 to 6 hours under at least one pressure chosen        from the range of the final pressure of Step (I) to 0.02 torr        absolute, in the presence of at least one thermal stabilizer        chosen from at least one of alkyl phosphate esters, aryl        phosphate esters, mixed alkyl aryl phosphate esters, reaction        products thereof, and mixtures thereof; to form a polyester;        wherein the total mole % of the dicarboxylic acid component of        the final polyester is 100 mole %; wherein the total mole % of        the glycol component of the final polyester is 100 mole %;        wherein the inherent viscosity of the final polyester is from        0.35 to 1.2 dL/g as determined in 60/40 (wt/wt)        phenol/tetrachloroethane at a concentration of 0.25 g/50 ml at        25° C.; and wherein the final polyester has a Tg of from 85 to        200° C.

In one aspect, the polyester compositions of the invention contain atleast one polycarbonate.

In one aspect, the polyester compositions of the invention contain nopolycarbonate.

In one aspect, the polyesters useful in the invention contain less than15 mole % ethylene glycol residues, such as, for example, 0.01 to lessthan 15 mole % ethylene glycol residues.

In one aspect, the polyesters useful in the invention contain noethylene glycol residues.

In one aspect, the polyesters useful in the invention contain 50 to99.99 mole % ethylene glycol residues.

In one aspect, the polyesters useful in the invention contain nobranching agent, or alternatively, at least one branching agent is addedeither prior to or during polymerization of the polyester.

In one aspect, the polyesters useful in the invention contain at leastone branching agent without regard to the method or sequence in which itis added.

In one aspect, the polyesters useful in the invention are made from no1,3-propanediol, or, 1,4-butanediol, either singly or in combination. Inother aspects, 1,3-propanediol or 1,4-butanediol, either singly or incombination, may be used in the making of the polyesters useful in thisinvention.

In one aspect of the invention, the mole % ofcis-2,2,4,4-tetramethyl-1,3-cyclobutanediol useful in certain polyestersuseful in the invention is greater than 50 mole % or greater than 55mole % of cis-2,2,4,4-tetramethyl-1,3-cyclobutanediol or greater than 70mole % of cis-2,2,4,4-tetramethyl-1,3-cyclobutanediol; wherein the totalmole percentage of cis-2,2,4,4-tetramethyl-1,3-cyclobutanediol andtrans-2,2,4,4-tetramethyl-1,3-cyclobutanediol is equal to a total of 100mole %.

In one aspect of the invention, the mole % of the isomers of2,2,4,4-tetramethyl-1,3-cyclobutanediol useful in certain polyestersuseful in the invention is from 30 to 70 mole % ofcis-2,2,4,4-tetramethyl-1,3-cyclobutanediol or from 30 to 70 mole % oftrans-2,2,4,4-tetramethyl-1,3-cyclobutanediol, or from 40 to 60 mole %of cis-2,2,4,4-tetramethyl-1,3-cyclobutanediol or from 40 to 60 mole %of trans-2,2,4,4-tetramethyl-1,3-cyclobutanediol, wherein the total molepercentage of cis-2,2,4,4-tetramethyl-1,3-cyclobutanediol andtrans-2,2,4,4-tetramethyl-1,3-cyclobutanediol is equal to a total of 100mole %.

In one aspect, certain polyesters useful in the invention may beamorphous or semicrystalline. In one aspect, certain polyesters usefulin the invention can have a relatively low crystallinity. Certainpolyesters useful in the invention can thus have a substantiallyamorphous morphology, meaning that the polyesters comprise substantiallyunordered regions of polymer.

In one aspect, the polyesters useful in the invention can comprise atleast one phosphorus compound whether or not present as a thermalstabilizer.

In one aspect, the polyesters useful in the invention can comprise atleast one thermal stabilizer which comprises at least one phosphoruscompound.

In one aspect, the polyesters and/or polyester compositions useful inthe invention can comprise phosphorus atoms.

In one aspect, the polyesters and/or polyester compositions useful inthe invention can comprise tin atoms.

In one embodiment, the polyesters useful in the invention can comprisephosphorus atoms and tin atoms.

In one aspect, the phosphorus compounds useful in the invention comprisephosphoric acid, phosphorous acid, phosphonic acid, phosphinic acid,phosphonous acid, and various esters and salts thereof. The esters canbe alkyl, branched alkyl, substituted alkyl, difunctional alkyl, alkylethers, aryl, and substituted aryl.

In one aspect, the phosphorus compounds useful in the invention compriseat least one thermal stabilizer chosen from at least one of substitutedor unsubstituted alkyl phosphate esters, substituted or unsubstitutedaryl phosphate esters, substituted or unsubstituted mixed alkyl arylphosphate esters, diphosphites, salts of phosphoric acid, phosphineoxides, and mixed aryl alkyl phosphites, reaction products thereof, andmixtures thereof. The phosphate esters include esters in which thephosphoric acid is fully esterified or only partially esterified.

In one aspect, the phosphorus compounds useful in the invention at leastone thermal stabilizer chosen from at least one of substituted orunsubstituted alkyl phosphate esters, substituted or unsubstituted arylphosphate esters, mixed substituted or unsubstituted alkyl arylphosphate esters, reaction products thereof, and mixtures thereof. Thephosphate esters include esters in which the phosphoric acid is fullyesterified or only partially esterified.

In one aspect, the phosphorus compounds useful in the invention arechosen from at least one of alkyl phosphate esters, aryl phosphateesters, mixed alkyl aryl phosphate esters, reaction products, thereof,and mixtures thereof.

In one aspect, any of the polyester compositions of the invention maycomprise at least one aryl phosphate ester.

In one aspect, any of the polyester compositions of the invention maycomprise at least one unsubstituted aryl phosphate ester.

In one aspect, any of the polyester compositions of the invention maycomprise at least one aryl phosphate ester which is not substituted withbenzyl groups.

In one aspect, any of the polyester compositions of the invention maycomprise at least one triaryl phosphate ester.

In one aspect, any of the polyester compositions of the invention maycomprise at least one triaryl phosphate ester which is not substitutedwith benzyl groups.

In one aspect, any of the polyester compositions of the invention maycomprise at least one alkyl phosphate ester.

In one aspect, any of the polyester compositions of the invention maycomprise triphenyl phosphate and/or Merpol A. In one embodiment, any ofthe polyester compositions of the invention may comprise triphenylphosphate.

In one aspect, the phosphorus compounds useful in the invention can bechosen from at least one of the following: diphosphites, salts ofphosphoric acid, phosphine oxides, and mixed aryl alkyl phosphites.

In one embodiment, the phosphorus compounds useful in the inventioncomprise, but are not limited to, at least one diphosphite.

In one embodiment, the phosphorus compounds useful in the inventioncomprise, but are not limited to, at least one diphosphite whichcontains a 2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane structure,such as, for example, Weston 619 (GE Specialty Chemicals, CAS#3806-34-6) and/or Doverphos S-9228 (Dover Chemicals, CAS# 154862-43-8).

In one aspect, the phosphorus compounds useful in the invention compriseat least one mixed alkyl aryl phosphite, such as, for example,bis(2,4-dicumylphenyl)pentaerythritol diphosphite also known asDoverphos S-9228 (Dover Chemicals, CAS# 154862-43-8).

In one embodiment, the phosphorus compounds useful in the inventioncomprise at least one phosphine oxide.

In one embodiment, the phosphorus compounds useful in the inventioncomprise at least one salt of phosphoric acid such as, for example,KH₂PO₄ and Zn₃(PO₄)₂.

In one aspect, any of processes described herein for making thepolyester compositions and/or polyesters comprise at least one of thephosphorus compounds described herein.

In one aspect, any of processes described herein for making any of thepolyester compositions and/or polyesters can comprise at least onediphosphite.

In one aspect, any of the processes described herein for making any ofthe polyester compositions and/or polyesters can comprise, at least onediphosphite which contains a2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane structure, such as,for example, Weston 619 (GE Specialty Chemicals, CAS# 3806-34-6) and/orDoverphos S-9228 (Dover Chemicals, CAS# 154862-43-8).

It is believed that any of the processes of making the polyesters usefulin the invention may be used to make any of the polyesters useful in theinvention.

In one aspect, the pressure used in Step (I) of any of the processes ofthe invention consists of at least one pressure chosen from 0 psig to 75psig. In one embodiment, the pressure used I Step (I) of any of theprocesses of the invention consists of at least one pressure chosen from0 psig to 50 psig.

In one aspect, the pressure used in Step (II) of any of the processes ofthe invention consists of at least one pressure chosen from 20 torrabsolute to 0.02 torr absolute; in one embodiment, the pressure used inStep (II) of any of the processes of the invention consists of at leastone pressure chosen from 10 torr absolute to 0.02 torr absolute; in oneembodiment, the pressure used in Step (II) of any of the processes ofthe invention consists of at least one pressure chosen from 5 torrabsolute to 0.02 torr absolute; in one embodiment, the pressure used inStep (II) of any of the processes of the invention consists of at leastone pressure chosen from 3 torr absolute to 0.02 torr absolute; in oneembodiment, the pressure used in Step (II) of any of the processes ofthe invention consists of at least one pressure chosen from 20 torrabsolute to 0.1 torr absolute; in one embodiment, the pressure used inStep (II) of any of the processes of the invention consists of at leastone pressure chosen from 10 torr absolute to 0.1-torr absolute; in oneembodiment, the pressure used in Step (II) of any of the processes ofthe invention consists of at least one pressure chosen from 5 torrabsolute to 0.1 torr absolute; in one embodiment, the pressure used inStep (II) of any of the processes of the invention consists of at leastone pressure chosen from 3 torr absolute to 0.1 torr absolute.

In one aspect, the molar ratio of glycol component/dicarboxylic acidcomponent added in Step (I) of any of the processes of the invention is1.0-1.5/1.0; in one aspect, the molar ratio of glycolcomponent/dicarboxylic acid component added in Step (I) of any of theprocesses of the invention is 1.01-1.5/1.0; in one aspect, the molarratio of glycol component/dicarboxylic acid component added in Step (I)of any of the processes of the invention is 1.01-1.3/1.0; in one aspect,the molar ratio of glycol component/dicarboxylic acid component added inStep (I) of any of the processes of the invention is 1.01-1.2/1.0; inone aspect, the molar ratio of glycol component/dicarboxylic acidcomponent added in Step (I) of any of the processes of the invention is1.01-1.15/1.0; in one aspect, the molar ratio of glycolcomponent/dicarboxylic acid component added in Step (I) of any of theprocesses of the invention is 1.01-1.10/1.0; in one aspect, the molarratio of glycol component/dicarboxylic acid component added in Step (I)of any of the processes of the invention is 1.03-1.5/1.0; in one aspect,the molar ratio of glycol component/dicarboxylic acid component added inStep (I) of any of the processes of the invention is 1.03-1.3/1.0; inone aspect, the molar ratio of glycol component/dicarboxylic acidcomponent added in Step (I) of any of the processes of the invention is1.03-1.2/1.0; in one aspect, the molar ratio of glycolcomponent/dicarboxylic acid component added in Step (I) of any of theprocesses of the invention is 1.03-1.15/1.0; in one aspect, the molarratio of glycol component/dicarboxylic acid component added in Step (I)of any of the processes of the invention is 1.03-1.10/1.0; in oneaspect, the molar ratio of glycol component/dicarboxylic acid componentadded in Step (I) of any of the processes of the invention is1.05-1.5/1.0; in one aspect, the molar ratio of glycolcomponent/dicarboxylic acid component added in Step (I) of any of theprocesses of the invention is 1.05-1.3/1.0; in one aspect, the molarratio of glycol component/dicarboxylic acid component added in Step (I)of any of the processes of the invention is 1.05-1.2/1.0; in one aspect,the molar ratio of glycol component/dicarboxylic acid component added inStep (I) of any of the processes of the invention is 1.05-1.15/1.0; andin one aspect, the molar ratio of glycol component/dicarboxylic acidcomponent added in Step (I) of any of the processes of the invention is1.01-1.10/1.0.

In any of the process embodiments for making the polyesters useful inthe invention, the heating time of Step (II) may be from 1 to 5 hours.In any of the process embodiments for making the polyesters useful inthe invention, the heating time of Step (II) may be from 1 to 4 hours.In any of the process embodiments for making the polyesters useful inthe invention, the heating time of Step (II) may be from 1 to 3 hours.In any of the process embodiments for making the polyesters useful inthe invention, the heating time of Step (II) may be from 1.5 to 3 hours.In any of the process embodiments for making the polyesters useful inthe invention, the heating time of Step (II) may be from 1 to 2 hours.

In another aspect, any of the polyester compositions and/or processes ofthe invention may comprise at least one tin compound as describedherein.

In one aspect, any of the polyester compositions and/or processes of theinvention may comprise at least one tin compound and, optionally, atleast one catalyst chosen from titanium, gallium, zinc, antimony,cobalt, manganese, magnesium, germanium, lithium, aluminum compounds andan aluminum compound with lithium hydroxide or sodium hydroxide.

In one embodiment, any of the polyester compositions and/or processes ofmaking the polyesters useful in the invention may be prepared using atleast one tin compound and at least one titanium compound as catalysts.

In one embodiment, the addition of the phosphorus compound(s) in theprocess(es) of the invention can result in a weight ratio of total tinatoms to total phosphorus atoms in the final polyester of 2-10:1. In oneembodiment, the addition of the phosphorus compound(s) in theprocess(es) can result in a weight ratio of total tin atoms to totalphosphorus atoms in the final polyester of 5-9:1. In one embodiment, theaddition of the phosphorus compound(s) in the process(es) can result ina weight ratio of total tin atoms to total phosphorus atoms in the finalpolyester of 6-8:1. In one embodiment, the addition of the phosphoruscompound(s) in the process(es) can result in a weight ratio of total tinatoms to total phosphorus atoms in the final polyester of 7:1.

In one embodiment, the amount of tin atoms in the final polyester usefulin the invention can be from 15 to 400 ppm tin atoms based on the weightof the final polyester.

In one embodiment, the amount of tin atoms in the final polyester usefulin the invention can be from 25 to 400 ppm tin atoms based on the weightof the final polyester.

In one embodiment, the amount of tin atoms in the final polyester usefulin the invention can be from 40 to 200 ppm tin atoms based on the weightof the final polyester.

In one embodiment, the amount of tin atoms in the final polyester usefulin the invention can be from 50 to 125 ppm tin atoms based on the weightof the final polyester.

In one embodiment, the amount of phosphorus atoms in the final polyesteruseful in the invention can be from 1 to 100 ppm phosphorus atoms basedon the weight of the final polyester.

In one embodiment, the amount of phosphorus atoms in the final polyesteruseful in the invention can be from 4 to 60 ppm phosphorus atoms basedon the weight of the final polyester.

In one embodiment, the amount of phosphorus atoms in the final polyesteruseful in the invention can be from 6 to 20 ppm phosphorus atoms basedon the weight of the final polyester.

In one embodiment, the amount of phosphorus atoms in the final polyesteruseful in the invention can be from 1 to 100 ppm phosphorus atoms basedon the weight of the final polyester and the amount of tin atoms in thefinal polyester can be from 15 to 400 ppm tin atoms based on the weightof the final polyester.

In one embodiment, the amount of phosphorus atoms in the final polyesteruseful in the invention can be from 1 to 100 ppm phosphorus atoms basedon the weight of the final polyester and the amount of tin atoms in thefinal polyester can be from 25 to 400 ppm tin atoms based on the weightof the final polyester.

In one embodiment, the amount of phosphorus atoms in the final polyesteruseful in the invention can be from 4 to 60 ppm phosphorus atoms basedon the weight of the final polyester and the amount of tin atoms in thefinal polyester can be from 40 to 200 ppm tin atoms based on the weightof the final polyester.

In one embodiment, the amount of phosphorus atoms in the final polyesteruseful in the invention can be from 6 to 20 ppm phosphorus atoms basedon the weight of the final polyester and the amount of tin atoms in thefinal polyester can be from 50 to 125 ppm tin atoms based on the weightof the final polyester.

In one aspect, any of the processes described herein for making any ofthe polyester compositions and/or polyesters can comprise at least onemixed alkyl aryl phosphites, such as, for example,bis(2,4-dicumylphenyl)pentaerythritol diphosphite also known asDoverphos S-9228 (Dover Chemicals, CAS# 154862-43-8).

In one aspect, any of the processes described herein for making any ofthe polyester compositions and/or polyesters can comprise, at least oneone phosphine oxide.

In one aspect, any of the processes described herein for making any ofthe polyester compositions and/or polyesters can comprise, at least onesalt of phosphoric acid such as, for example, KH₂PO₄ and Zn₃(PO₄)₂.

In one aspect, the polyester compositions are useful in articles ofmanufacture including, but not limited to, extruded, calendered, and/ormolded articles including, but not limited to, injection moldedarticles, extruded articles, cast extrusion articles, profile extrusionarticles, melt spun articles, thermoformed articles, extrusion moldedarticles, injection blow molded articles, injection stretch blow moldedarticles, extrusion blow molded articles and extrusion stretch blowmolded articles. These articles can include, but are not limited to,films, bottles, containers, sheet and/or fibers.

In one aspect, the polyester compositions useful in the invention may beused in various types of film and/or sheet, including but not limited toextruded film(s) and/or sheet(s), calendered film(s) and/or sheet(s),compression molded film(s) and/or sheet(s), solution casted film(s)and/or sheet(s). Methods of making film and/or sheet include but are notlimited to extrusion, calendering, compression molding, and solutioncasting.

Also, in one aspect, use of these particular polyester compositionsminimizes and/or eliminates the drying step prior to melt processingand/or thermoforming.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graph showing the effect of comonomer on the fastestcrystallization half-times of modified PCT copolyesters.

FIG. 2 is a graph showing the effect of comonomer on thebrittle-to-ductile transition temperature (T_(bd)) in a notched Izodimpact strength test ASTM D256, ⅛-in thick, 10-mil notch).

FIG. 3 is a graph showing the effect of2,2,4,4-tetramethyl-1,3-cyclobutanediol composition on the glasstransition temperature (Tg) of the copolyester.

DETAILED DESCRIPTION OF THE INVENTION

The present invention may be understood more readily by reference to thefollowing detailed description of certain embodiments of the inventionand the working examples. In accordance with the purpose(s) of thisinvention, certain embodiments of the invention are described in theSummary of the Invention and are further described herein below. Also,other embodiments of the invention are described herein.

It is believed that polyesters useful in the invention described hereincan have a combination of two or more physical properties such as highimpact strengths, moderate glass transition temperatures (Tg or Tg),chemical resistance, hydrolytic stability, toughness, lowductile-to-brittle transition temperatures, good color and clarity, lowdensities, long crystallization half-times, and good processabilitythereby easily permitting them to be formed into articles. In some ofthe embodiments of the invention, the polyesters have a uniquecombination of the properties of good impact strength, heat resistance,chemical resistance, density and/or the combination of the properties ofgood impact strength, heat resistance, and processability and/or thecombination of two or more of the described properties, that have neverbefore been believed to be present in a polyester.

The term “polyester”, as used herein, is intended to include“copolyesters” and is understood to mean a synthetic polymer prepared bythe reaction of one or more difunctional carboxylic acids and/ormultifunctional carboxylic acids with one or more difunctional hydroxylcompounds and/or multifunctional hydroxyl compounds. Typically thedifunctional carboxylic acid can be a dicarboxylic acid and thedifunctional hydroxyl compound can be a dihydric alcohol such as, forexample, glycols and diols. The term “glycol” as used in thisapplication includes, but is not limited to, diols, glycols, and/ormultifunctional hydroxyl compounds, for example, branching agents.Alternatively, the difunctional carboxylic acid may be a hydroxycarboxylic acid such as, for example, p-hydroxybenzoic acid, and thedifunctional hydroxyl compound may be an aromatic nucleus bearing 2hydroxyl substituents such as, for example, hydroquinone. The term“residue”, as used herein, means any organic structure incorporated intoa polymer through a polycondensation and/or an esterification reactionfrom the corresponding monomer. The term “repeating unit”, as usedherein, means an organic structure having a dicarboxylic acid residueand a diol residue bonded through a carbonyloxy group. Thus, forexample, the dicarboxylic acid residues may be derived from adicarboxylic acid monomer or its associated acid halides, esters, salts,anhydrides, or mixtures thereof. As used herein, therefore, the termdicarboxylic acid is intended to include dicarboxylic acids and anyderivative of a dicarboxylic acid, including its associated acidhalides, esters, half-esters, salts, half-salts, anhydrides, mixedanhydrides, or mixtures thereof, useful in a reaction process with adiol to make polyester. Furthermore, as used in this application, theterm “diacid” includes multifunctional acids, for example, branchingagents. As used herein, the term “terephthalic acid” is intended toinclude terephthalic acid itself and residues thereof as well as anyderivative of terephthalic acid, including its associated acid halides,esters, half-esters, salts, half-salts, anhydrides, mixed anhydrides, ormixtures thereof or residues thereof useful in a reaction process with adiol to make polyester.

In one embodiment, terephthalic acid may be used as the startingmaterial. In another embodiment, dimethyl terephthalate may be used asthe starting material. In yet another embodiment, mixtures ofterephthalic acid and dimethyl terephthalate may be used as the startingmaterial and/or as an intermediate material.

The polyesters used in the present invention typically can be preparedfrom dicarboxylic acids and diols which react in substantially equalproportions and are incorporated into the polyester polymer as theircorresponding residues. The polyesters of the present invention,therefore, can contain substantially equal molar proportions of acidresidues (100 mole %) and diol (and/or multifunctional hydroxylcompounds) residues (100 mole %) such that the total moles of repeatingunits is equal to 100 mole %. The mole percentages provided in thepresent disclosure, therefore, may be based on the total moles of acidresidues, the total moles of diol residues, or the total moles ofrepeating units. For example, a polyester containing 30 mole %isophthalic acid, based on the total acid residues, means the polyestercontains 30 mole % isophthalic acid residues out of a total of 100 mole% acid residues. Thus, there are 30 moles of isophthalic acid residuesamong every 100 moles of acid residues. In another example, a polyestercontaining 30 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol, based onthe total diol residues, means the polyester contains 30 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues out of a total of 100mole % diol residues. Thus, there are 30 moles of2,2,4,4-tetramethyl-1,3-cyclobutanediol residues among every 100 molesof diol residues.

In other aspects of the invention, the Tg of the polyesters useful inthe invention can be at least one of the following ranges: 85 to 130°C.; 85 to 125° C.; 85 to 120° C.; 85 to 115° C.; 85 to 110° C.; 85 to105° C.; 85 to 100° C.; 85 to 95° C.; 85 to 90° C.; 90 to 130° C.; 90 to125° C.; 90 to 120° C.; 90 to 115° C.; 90 to 110° C.; 90 to 105° C.; 90to 100° C.; 90 to 95° C.; 95 to 130° C.; 95 to 125° C.; 95 to 120° C.;95 to 115° C.; 95 to 110° C.; 95 to 105° C.; 95 to 100° C.; 100 to 130°C.; 100 to 125° C.; 100 to 120° C.; 100 to 115° C.; 100 to 110° C.; 100to 105° C.; 105 to 130° C.; 105 to 125° C.; 105 to 120° C.; 105 to 115°C.; 105 to 110° C.; greater than 105 to 130° C.; greater than 105 to125° C.; greater than 105 to 120° C.; greater than 105 to 115° C.;greater than 105 to 110° C.; 110 to 130° C.; 110 to 125° C.; 110 to 120°C.; 110 to 115° C.; 115 to 130° C.; 115 to 125° C.; 115 to 120° C.; 115to 130° C.; 115 to 125° C.; 115 to 120° C.; 120 to 130° C.; and 125 to130° C.

In other aspects of the invention, the glycol component for thepolyesters useful in the invention include but are not limited to atleast one of the following combinations of ranges: 1 to 99 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1 to 99 mole %cyclohexanedimethanol; 1 to 95 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 5 to 99 mole %cyclohexanedimethanol; 1 to 90 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10 to 99 mole %cyclohexanedimethanol; 1 to 85 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15 to 99 mole %cyclohexanedimethanol; 1 to 80 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20 to 99 mole %cyclohexanedimethanol, 1 to 75 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25 to 99 mole %cyclohexanedimethanol; 1 to 70 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30 to 99 mole %cyclohexanedimethanol; 1 to 65 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35 to 99 mole %cyclohexanedimethanol; 1 to 60 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 40 to 99 mole %cyclohexanedimethanol; 1 to 55 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 45 to 99 mole %cyclohexanedimethanol; 1 to 50 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 50 to 99 mole %cyclohexanedimethanol; 1 to 45 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 55 to 99 mole %cyclohexanedimethanol; 1 to 40 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 60 to 99 mole %cyclohexanedimethanol; 1 to 35 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 65 to 99 mole %cyclohexanedimethanol; 1 to 30 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 70 to 99 mole %cyclohexanedimethanol; 1 to 25 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 75 to 99 mole %cyclohexanedimethanol; 1 to 20 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 80 to 99 mole %cyclohexanedimethanol; 1 to 15 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 85 to 99 mole %cyclohexanedimethanol; 1 to 10 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 90 to 99 mole %cyclohexanedimethanol; and 1 to 5 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 95 to 99 mole %cyclohexanedimethanol; greater than 0.01 to 10 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 90 to less than 99.99 mole %cyclohexanedimethanol; and greater than 0.01 to 5 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 95 to less than 99.99 mole %cyclohexanedimethanol.

In other aspects of the invention, the glycol component for thepolyesters useful in the film or sheet of the invention include but arenot limited to at least one of the following combinations of ranges: 5to 99 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1 to 95 mole %cyclohexanedimethanol; 5 to 95 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 5 to 95 mole %cyclohexanedimethanol; 5 to 90 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10 to 95 mole %cyclohexanedimethanol; 5 to 85 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15 to 95 mole %cyclohexanedimethanol; 5 to 80 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20 to 95 mole %cyclohexanedimethanol, 5 to 75 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25 to 95 mole %cyclohexanedimethanol; 5 to 70 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30 to 95 mole %cyclohexanedimethanol; 5 to 65 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35 to 95 mole %cyclohexanedimethanol; 5 to 60 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 40 to 95 mole %cyclohexanedimethanol; 5 to 55 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 45 to 95 mole %cyclohexanedimethanol; and 5 to 50 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 50 to 95 mole %cyclohexanedimethanol.

In other aspects of the invention, the glycol component for thepolyesters useful in the invention include but are not limited to atleast one of the following combinations of ranges: 5 to less than 50mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and greater than 50 to 95mole % cyclohexanedimethanol; 5 to 45 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 55 to 95 mole %cyclohexanedimethanol; 5 to 40 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 60 to 95 mole %cyclohexanedimethanol; 5 to 35 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 65 to 95 mole %cyclohexanedimethanol; 5 to less than 35 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and greater than 65 to 95 mole %cyclohexanedimethanol; 5 to 30 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 70 to 95 mole %cyclohexanedimethanol; 5 to 25 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 75 to 95 mole %cyclohexanedimethanol; 5 to 20 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 80 to 95 mole %cyclohexanedimethanol; 5 to 15 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 85 to 95 mole %cyclohexanedimethanol; and 5 to 10 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 75 to 90 mole %cyclohexanedimethanol.

In other aspects of the invention, the glycol component for thepolyesters useful in the film or sheet of the invention include but arenot limited to at least one of the following combinations of ranges: 10to 99 mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1 to 90 mole %cyclohexanedimethanol; 10 to 95 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 5 to 90 mole %cyclohexanedimethanol; 10 to 90 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10 to 90 mole %cyclohexanedimethanol; 10 to 85 mole % 2,2,4,4tetramethyl-1,3-cyclobutanediol and 15 to 90 mole %cyclohexanedimethanol; 10 to 80 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20 to 90 mole %cyclohexanedimethanol, 10 to 75 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25 to 90 mole %cyclohexanedimethanol; 10 to 70 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30 to 90 mole %cyclohexanedimethanol; 10 to 65 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35 to 90 mole %cyclohexanedimethanol; 10 to 60 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 40 to 90 mole %cyclohexanedimethanol; 10 to 55 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 45 to 90 mole %cyclohexanedimethanol; and 10 to 50 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 50 to 90 mole %cyclohexanedimethanol.

In other aspects of the invention, the glycol component for thepolyesters useful in the invention include but are not limited to atleast one of the following combinations of ranges: 10 to less than 50mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and greater than 50 to 90mole % cyclohexanedimethanol; 10 to 45 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 55 to 90 mole %cyclohexanedimethanol; 10 to 40 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 60 to 90 mole %cyclohexanedimethanol; 10 to 35 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 65 to 90 mole %cyclohexanedimethanol; 10 to less than 35 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and greater than 65 up to 90mole % cyclohexanedimethanol; 10 to 30 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 70 to 90 mole %cyclohexanedimethanol; 10 to 25 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and greater than 75 to 90 mole %cyclohexanedimethanol. 10 to 20 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and greater than 80 to 90 mole %cyclohexanedimethanol; and 10 to 15 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and greater than 85 to 90 mole %cyclohexanedimethanol.

In other aspects of the invention, the glycol component for thepolyesters useful in the invention include but are not limited to atleast one of the following combinations of ranges: 11 to 99 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1 to 89 mole %cyclohexanedimethanol; 11 to 95 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 5 to 89 mole %cyclohexanedimethanol; 11 to 90 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10 to 89 mole %cyclohexanedimethanol; 11 to 85 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15 to 89 mole %cyclohexanedimethanol; 11 to 80 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20 to 89 mole %cyclohexanedimethanol, 11 to 75 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25 to 89 mole %cyclohexanedimethanol; 11 to 70 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30 to 89 mole %cyclohexanedimethanol; 11 to 65 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35 to 89 mole %cyclohexanedimethanol; 11 to 60 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 40 to 89 mole %cyclohexanedimethanol; 11 to 55 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 45 to 89 mole %cyclohexanedimethanol; and 11 to 50 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 50 to 89 mole %cyclohexanedimethanol.

In other aspects of the invention, the glycol component for thepolyesters useful in the invention include but are not limited to atleast one of the following combinations of ranges: 11 to less than 50mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and greater than 50 up to89 mole % cyclohexanedimethanol; 11 to 45 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 55 to 89 mole %cyclohexanedimethanol; 11 to 40 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 60 to 89 mole %cyclohexanedimethanol; 11 to 35 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 65 to 89 mole %cyclohexanedimethanol; 11 to 30 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 70 to 89 mole %cyclohexanedimethanol; 11 to 25 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 75 to 89 mole %cyclohexanedimethanol; 11 to 20 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 80 to 89 mole %cyclohexanedimethanol, and 11 to 15 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 80 to 85 mole %cyclohexanedimethanol.

In other aspects of the invention, the glycol component for thepolyesters useful in the invention include but are not limited to atleast one of the following combinations of ranges: 12 to 99 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1 to 86 mole %cyclohexanedimethanol; 12 to 95 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 5 to 88 mole %cyclohexanedimethanol; 12 to 90 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10 to 88 mole %cyclohexanedimethanol; 12 to 85 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15 to 88 mole %cyclohexanedimethanol; 12 to 86 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 14 to 88 mole %cyclohexanedimethanol, 12 to 75 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25 to 88 mole %cyclohexanedimethanol; 12 to 70 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30 to 88 mole %cyclohexanedimethanol; 12 to 65 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35 to 88 mole %cyclohexanedimethanol; 12 to 60 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 40 to 88 mole %cyclohexanedimethanol; 12 to 55 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 45 to 88 mole %cyclohexanedimethanol; and 12 to 50 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 50 to 88 mole %cyclohexanedimethanol;

In other aspects of the invention, the glycol component for thepolyesters useful in the invention include but are not limited to atleast one of the following combinations of ranges: 12 to less than 50mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and greater than 50 up to88 mole % cyclohexanedimethanol; 12 to 45 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 55 to 88 mole %cyclohexanedimethanol; 12 to 40 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 60 to 88 mole %cyclohexanedimethanol; 12 to 35 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 65 to 88 mole %cyclohexanedimethanol; 12 to 30 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 70 to 88 mole %cyclohexanedimethanol; 12 to 25 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 75 to 88 mole %cyclohexanedimethanol; 12 to 20 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 80 to 88 mole %cyclohexanedimethanol, and 12 to 15 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol; and 85 to 88 mole %cyclohexanedimethanol.

In other aspects of the invention, the glycol component for thepolyesters useful in the invention include but are not limited to atleast one of the following combinations of ranges: 13 to 99 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1 to 87 mole %cyclohexanedimethanol; 13 to 95 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 5 to 87 mole %cyclohexanedimethanol; 13 to 90 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10 to 87 mole %cyclohexanedimethanol; 13 to 85 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15 to 87 mole %cyclohexanedimethanol; 13 to 80 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20 to 87 mole %cyclohexanedimethanol, 13 to 75 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25 to 87 mole %cyclohexanedimethanol; 13 to 70 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30 to 87 mole %cyclohexanedimethanol; 13 to 65 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35 to 87 mole %cyclohexanedimethanol; 13 to 60 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 40 to 87 mole %cyclohexanedimethanol; 13 to 55 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 45 to 87 mole %cyclohexanedimethanol; and 13 to 50 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 50 to 87 mole %cyclohexanedimethanol.

In other aspects of the invention, the glycol component for thepolyesters useful in the invention include but are not limited to atleast one of the following combinations of ranges: 13 to less than 50mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and greater than 50 up to87 mole % cyclohexanedimethanol; 13 to 45 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 55 to 87 mole %cyclohexanedimethanol; 13 to 40 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 60 to 87 mole %cyclohexanedimethanol; 13 to 35 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 65 to 87 mole %cyclohexanedimethanol; 13 to 30 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 70 to 87 mole %cyclohexanedimethanol; 13 to 25 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 75 to 87 mole %cyclohexanedimethanol; 13 to 20 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 80 to 87 mole %cyclohexanedimethanol, and 13 to 15 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol; and 85 to 87 mole %cyclohexanedimethanol.

In other aspects of the invention, the glycol component for thepolyesters useful in the invention include but are not limited to atleast one of the following combinations of ranges: 14 to 99 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1 to 86 mole %cyclohexanedimethanol; 14 to 95 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 5 to 86 mole %cyclohexanedimethanol; 14 to 90 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10 to 86 mole %cyclohexanedimethanol; 14 to 85 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15 to 86 mole %cyclohexanedimethanol; 14 to 86 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 14 to 86 mole %cyclohexanedimethanol, 14 to 75 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25 to 86 mole %cyclohexanedimethanol; 14 to 70 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30 to 86 mole %cyclohexanedimethanol; 14 to 65 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35 to 86 mole %cyclohexanedimethanol; 14 to 60 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 40 to 86 mole %cyclohexanedimethanol; 14 to 55 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 45 to 86 mole %cyclohexanedimethanol; and 14 to 50 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 50 to 86 mole %cyclohexanedimethanol;

In other aspects of the invention, the glycol component for thepolyesters useful in the invention include but are not limited to atleast one of the following combinations of ranges: 14 to less than 50mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and greater than 50 up to86 mole % cyclohexanedimethanol; 14 to 45 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 55 to 86 mole %cyclohexanedimethanol; 14 to 40 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 60 to 86 mole %cyclohexanedimethanol; 14 to 35 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 65 to 86 mole %cyclohexanedimethanol; 14 to 30 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 70 to 86 mole %cyclohexanedimethanol; 14 to 25 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 75 to 86 mole %cyclohexanedimethanol; and 14 to 20 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 80 to 86 mole %cyclohexanedimethanol.

In other aspects of the invention, the glycol component for thepolyesters useful in the invention include but are not limited to atleast one of the following combinations of ranges: 15 to 99 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1 to 85 mole %cyclohexanedimethanol; 15 to 95 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 5 to 85 mole %cyclohexanedimethanol; 15 to 90 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10 to 85 mole %cyclohexanedimethanol; 15 to 85 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15 to 85 mole %cyclohexanedimethanol; 15 to 85 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15 to 85 mole %cyclohexanedimethanol, 15 to 75 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25 to 85 mole %cyclohexanedimethanol; 15 to 70 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30 to 85 mole %1,4-cyclohexanedimethanol; 15 to 65 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35 to 85 mole %cyclohexanedimethanol; 15 to 60 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 40 to 85 mole %cyclohexanedimethanol; 15 to 55 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 45 to 85 mole %cyclohexanedimethanol; and 15 to 50 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 50 to 85 mole %cyclohexanedimethanol.

In other aspects of the invention, the glycol component for thepolyesters useful in the invention include but are not limited to atleast one of the following combinations of ranges: 15 to less than 50mole % 2,2,4,4-tetramethyl-1,3-cyclobutanediol and greater than 50 up to85 mole % cyclohexanedimethanol; 15 to 45 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 55 to 85 mole %cyclohexanedimethanol; 15 to 40 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 60 to 85 mole %cyclohexanedimethanol; 15 to 35 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 65 to 85 mole %cyclohexanedimethanol; 15 to 30 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 70 to 85 mole %cyclohexanedimethanol; 15 to 25 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 75 to 85 mole %cyclohexanedimethanol; 15 to 20 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 80 to 85 mole %cyclohexanedimethanol; and 17 to 23 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 77 to 83 mole %cyclohexanedimethanol.

In other aspects of the invention, the glycol component for thepolyesters useful in the invention include but are not limited to atleast one of the following combinations of ranges: 20 to 99 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1 to 80 mole %cyclohexanedimethanol; 20 to 95 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 5 to 80 mole %cyclohexanedimethanol; 20 to 90 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10 to 80 mole %cyclohexanedimethanol; 20 to 85 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15 to 80 mole %cyclohexanedimethanol; 20 to 80 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20 to 80 mole %cyclohexanedimethanol, 20 to 75 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25 to 80 mole %cyclohexanedimethanol; 20 to 70 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30 to 80 mole %cyclohexanedimethanol; 20 to 65 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35 to 80 mole %cyclohexanedimethanol; 20 to 60 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 40 to 80 mole %cyclohexanedimethanol; 20 to 55 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 45 to 80 mole %cyclohexanedimethanol; 20 to 50 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 50 to 80 mole %cyclohexanedimethanol; 20 to 45 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 55 to 80 mole %cyclohexanedimethanol; 20 to 40 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 60 to 80 mole %cyclohexanedimethanol; 20 to 35 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 65 to 80 mole %cyclohexanedimethanol; 20 to 30 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 70 to 80 mole %cyclohexanedimethanol; and 20 to 25 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 75 to 80 mole %cyclohexanedimethanol.

In other aspects of the invention, the glycol component for thepolyesters useful in the invention include but are not limited to atleast one of the following combinations of ranges: 25 to 99 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1 to 75 mole %cyclohexanedimethanol; 25 to 90 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 10 to 75 mole %cyclohexanedimethanol; 25 to 85 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 15 to 75 mole %cyclohexanedimethanol; 25 to 80 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20 to 75 mole %cyclohexanedimethanol, 25 to 75 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25 to 75 mole %cyclohexanedimethanol; 25 to 70 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30 to 75 mole %cyclohexanedimethanol; 25 to 65 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35 to 75 mole %cyclohexanedimethanol; 25 to 60 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 40 to 75 mole %cyclohexanedimethanol; 25 to 55 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 45 to 75 mole %cyclohexanedimethanol; 25 to 50 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 50 to 75 mole %cyclohexanedimethanol; 25 to 45 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 55 to 75 mole %cyclohexanedimethanol; 25 to 40 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 60 to 75 mole %cyclohexanedimethanol; 25 to 35 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 65 to 75 mole %cyclohexanedimethanol; 25 to 30 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 70 to 75 mole %cyclohexanedimethanol.

In other aspects of the invention, the glycol component for thepolyesters useful in the invention include but are not limited to atleast one of the following combinations of ranges: 35 to 80 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20 to 65 mole %cyclohexanedimethanol; 37 to 80 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20 to 63 mole %cyclohexanedimethanol; 40 to 80 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20 to 60 mole %cyclohexanedimethanol; 45 to 80 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20 to 55 mole %cyclohexanedimethanol; 50 to 80 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20 to 50 mole %cyclohexanedimethanol; greater than 50 to 80 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20 to less than 50 mole %cyclohexanedimethanol; 55 to 80 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20 to 45 mole %cyclohexanedimethanol; 60 to 80 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20 to 40 mole %cyclohexanedimethanol; 65 to 80 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20 to 35 mole %cyclohexanedimethanol; 70 to 80 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20 to 30 mole %cyclohexanedimethanol; 40 to 75 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25 to 60 mole %cyclohexanedimethanol; 45 to 75 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25 to 55 mole %cyclohexanedimethanol; 50 to 75 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25 to 50 mole %cyclohexanedimethanol; 55 to 75 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25 to 45 mole %cyclohexanedimethanol; 60 to 75 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25 to 40 mole %cyclohexanedimethanol; 65 to 75 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25 to 35 mole %cyclohexanedimethanol; 40 to 70 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30 to 60 mole %cyclohexanedimethanol; 45 to 70 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30 to 55 mole %cyclohexanedimethanol; 50 to 70 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30 to 50 mole %cyclohexanedimethanol; greater than 50 to 99 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1 to less than 50 mole %cyclohexanedimethanol; greater than 50 to 80 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 20 to less than 50 mole %cyclohexanedimethanol; greater than 50 to 75 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 25 to less than 50 mole %cyclohexanedimethanol; greater than 50 to 70 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30 to less than 50 mole %cyclohexanedimethanol; 55 to 70 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30 to 45 mole %cyclohexanedimethanol; 60 to 70 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 30 to 40 mole %cyclohexanedimethanol; 40 to 65 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35 to 60 mole %cyclohexanedimethanol; 40 to 55 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 45 to 60 mole %cyclohexanedimethanol; 40 to less than 45 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and greater than 55 to 60 mole %cyclohexanedimethanol; 45 to 65 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35 to 55 mole %cyclohexanedimethanol; greater than 50 to 65 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35 to less than 50 mole %cyclohexanedimethanol; 50 to 65 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35 to 50 mole %cyclohexanedimethanol; 55 to 65 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35 to 45 mole %cyclohexanedimethanol; 40 to 60 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 40 to 60 mole %cyclohexanedimethanol; 45 to 60 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 40 to 55 mole %cyclohexanedimethanol; 45 to 55 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 45 to 55 mole %cyclohexanedimethanol; greater than 45 to 55 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol; 45 to less than 55 mole %cyclohexanedimethanol; and 46 to 55 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 45 to 54 mole %cyclohexanedimethanol; and 46 to 65 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol and 35 to 54 mole %cyclohexanedimethanol.

In addition to the diols set forth above, the polyesters useful in thepolyester compositions of the invention may also be made from1,3-propanediol, 1,4-butanediol, or mixtures thereof.

In addition to the diols set forth above, the polyesters useful in thepolyester compositions of the invention may also be made from1,3-propanediol, 1,4-butanediol, or mixtures thereof can possess atleast one of the Tg ranges described herein, at least one of theinherent viscosity ranges described herein, and/or at least one of theglycol or diacid ranges described herein. In addition or in thealternative, the polyesters useful in the invention can be made from1,3-propanediol or 1,4-butanediol or mixtures thereof may also be madefrom 1,4-cyclohexanedmethanol in at least one of the following amounts:from 0.1 to 99 mole %; from 0.1 to 95 mole %; from 0.1 to 90 mole %;from 0.1 to 85 mole %; from 0.1 to 80 mole %; from 0.1 to 70 mole %;from 0.1 to 60 mole %; from 0.1 to 50 mole %; from 0.1 to 40 mole %;from 0.1 to 35 mole %; from 0.1 to 30 mole %; from 0.1 to 25 mole %;from 0.1 to 20 mole %; from 0.1 to 15 mole %; from 0.1 to 10 mole %;from 0.1 to 5 mole %; from 1 to 99 mole %; 1 to 95 mole %; from 1 to 90mole %; from 1 to 85 mole %; from 1 to 80 mole %; from 1 to 70 mole %;from 1 to 60 mole %; from 1 to 50 mole %; from 1 to 40 mole %; from 1 to35 mole %; from 1 to 30 mole %; from 1 to 25 mole %; from 1 to 20 mole%; from 1 to 15 mole %; from 1 to 10 mole %; from 1 to 5 mole %; 5 to 99mole %; 5 to 95 mole %; from 5 to 90 mole %; from 5 to 85 mole %; from 5to 80 mole %; 5 to 70 mole %; from 5 to 60 mole %; from 5 to 50 mole %;from 5 to 40 mole %; from 5 to 35 mole %; from 5 to 30 mole %; from 5 to25 mole %; from 5 to 20 mole %; and from 5 to 15 mole %; from 5 to 10mole %; from 10 to 99 mole %; 10 to 95 mole %; from 10 to 90 mole %;from 10 to 85 mole %; from 10 to 80 mole %; from 10 to 70 mole %; from10 to 60 mole %; from 10 to 50 mole %; from 10 to 40 mole %; from 10 to35 mole %; from 10 to 30 mole %; from 10 to 25 mole %; from 10 to 20mole %; from 10 to 15 mole %; from 20 to 99 mole %; 20 to 95 mole %;from 20 to 90 mole %; from 20 to 85 mole %; from 20 to 80 mole %; from20 to 70 mole %; from 20 to 60 mole %; from 20 to 50 mole %; from 20 to40 mole %; from 20 to 35 mole %; from 20 to 30 mole %; and from 20 to 25mole %.

For certain embodiments of the invention, the polyesters useful in theinvention may exhibit at least one of the following inherent viscositiesas determined in 60/40 (wt/wt) phenol/tetrachloroethane at aconcentration of 0.25 g/50 ml at 25° C.: 0.10 to 1.2 dL/g; 0.10 to 1.1dL/g; 0.10 to 1 dL/g; 0.10 to less than 1 dL/g; 0.10 to 0.98 dL/g; 0.10to 0.95 dL/g; 0.10 to 0.90 dL/g; 0.10 to 0.85 dL/g; 0.10 to 0.80 dL/g;0.10 to 0.75 dL/g; 0.10 to less than 0.75 dL/g; 0.10 to 0.72 dL/g; 0.10to 0.70 dL/g; 0.10 to less than 0.70 dL/g; 0.10 to 0.68 dL/g; 0.10 toless than 0.68 dL/g; 0.10 to 0.65 dL/g; 0.20 to 1.2 dL/g; 0.20 to 1.1dL/g; 0.20 to 1 dL/g; 0.20 to less than 1 dL/g; 0.20 to 0.98 dL/g; 0.20to 0.95 dL/g; 0.20 to 0.90 dL/g; 0.20 to 0.85 dL/g; 0.20 to 0.80 dL/g;0.20 to 0.75 dL/g; 0.20 to less than 0.75 dL/g; 0.20 to 0.72 dL/g; 0.20to 0.70 dL/g; 0.20 to less than 0.70 dL/g; 0.20 to 0.68 dL/g; 0.20 toless than 0.68 dL/g; 0.20 to 0.65 dL/g; 0.35 to 1.2 dL/g; 0.35 to 1.1dL/g; 0.35 to 1 dL/g; 0.35 to less than 1 dL/g; 0.35 to 0.98 dL/g; 0.35to 0.95 dL/g; 0.35 to 0.90 dL/g; 0.35 to 0.85 dL/g; 0.35 to 0.80 dL/g;0.35 to 0.75 dL/g; 0.35 to less than 0.75 dL/g; 0.35 to 0.72 dL/g; 0.35to 0.70 dL/g; 0.35 to less than 0.70 dL/g; 0.35 to 0.68 dL/g; 0.35 toless than 0.68 dL/g; 0.35 to 0.65 dL/g; 0.40 to 1.2 dL/g; 0.40 to 1.1dL/g; 0.40 to I dL/g; 0.40 to less than 1 dL/g; 0.40 to 0.98 dL/g; 0.40to 0.95 dL/g; 0.40 to 0.90 dL/g; 0.40 to 0.85 dL/g; 0.40 to 0.80 dL/g;0.40 to 0.75 dL/g; 0.40 to less than 0.75 dL/g; 0.40 to 0.72 dL/g; 0.40to 0.70 dL/g; 0.40 to less than 0.70 dL/g; 0.40 to 0.68 dL/g; 0.40 toless than 0.68 dL/g; 0.40 to 0.65 dL/g; greater than 0.42 to 1.2 dL/g;greater than 0.42 to 1.1 dL/g; greater than 0.42 to 1 dL/g; greater than0.42 to less than 1 dL/g; greater than 0.42 to 0.98 dL/g; greater than0.42 to 0.95 dL/g; greater than 0.42 to 0.90 dL/g; greater than 0.42 to0.85 dL/g; greater than 0.42 to 0.80 dL/g; greater than 0.42 to 0.75dL/g; greater than 0.42 to less than 0.75 dL/g; greater than 0.42 to0.72 dL/g; greater than 0.42 to less than 0.70 dL/g; greater than 0.42to 0.68 dL/g; greater than 0.42 to less than 0.68 dL/g; and greater than0.42 to 0.65 dL/g.

For certain embodiments of the invention, the polyesters useful in theinvention may exhibit at least one of the following inherent viscositiesas determined in 60/40 (wt/wt) phenol/tetrachloroethane at aconcentration of 0.25 g/50 ml at 25° C.: 0.45 to 1.2 dL/g; 0.45 to 1.1dL/g; 0.45 to 1 dL/g; 0.45 to 0.98 dL/g; 0.45 to 0.95 dL/g; 0.45 to 0.90dL/g; 0.45 to 0.85 dL/g; 0.45 to 0.80 dL/g; 0.45 to 0.75 dL/g; 0.45 toless than 0.75 dL/g; 0.45 to 0.72 dL/g; 0.45 to 0.70 dL/g; 0.45 to lessthan 0.70 dL/g; 0.45 to 0.68 dL/g; 0.45 to less than 0.68 dL/g; 0.45 to0.65 dL/g; 0.50 to 1.2 dL/g; 0.50 to 1.1 dL/g; 0.50 to 1 dL/g; 0.50 toless than 1 dL/g; 0.50 to 0.98 dL/g; 0.50 to 0.95 dL/g; 0.50 to 0.90dL/g; 0.50 to 0.85 dL/g; 0.50 to 0.80 dL/g; 0.50 to 0.75 dL/g; 0.50 toless than 0.75 dL/g; 0.50 to 0.72 dL/g; 0.50 to 0.70 dL/g; 0.50 to lessthan 0.70 dL/g; 0.50 to 0.68 dL/g; 0.50 to less than 0.68 dL/g; 0.50 to0.65 dL/g; 0.55 to 1.2 dL/g; 0.55 to 1.1 dL/g; 0.55 to 1 dL/g; 0.55 toless than 1 dL/g; 0.55 to 0.98 dL/g; 0.55 to 0.95 dL/g; 0.55 to 0.90dL/g; 0.55 to 0.85 dL/g; 0.55 to 0.80 dL/g; 0.55 to 0.75 dL/g; 0.55 toless than 0.75 dL/g; 0.55 to 0.72 dL/g; 0.55 to 0.70 dL/g; 0.55 to lessthan 0.70 dL/g; 0.55 to 0.68 dL/g; 0.55 to less than 0.68 dL/g; 0.55 to0.65 dL/g; 0.58 to 1.2 dL/g; 0.58 to 1.1 dL/g; 0.58 to 1 dL/g; 0.58 toless than 1 dL/g; 0.58 to 0.98 dL/g; 0.58 to 0.95 dL/g; 0.58 to 0.90dL/g; 0.58 to 0.85 dL/g; 0.58 to 0.80 dL/g; 0.58 to 0.75 dL/g; 0.58 toless than 0.75 dL/g; 0.58 to 0.72 dL/g; 0.58 to 0.70 dL/g; 0.58 to lessthan 0.70 dL/g; 0.58 to 0.68 dL/g; 0.58 to less than 0.68 dL/g; 0.58 to0.65 dL/g; 0.60 to 1.2 dL/g; 0.60 to 1.1 dL/g; 0.60 to 1 dL/g; 0.60 toless than 1 dL/g; 0.60 to 0.98 dL/g; 0.60 to 0.95 dL/g; 0.60 to 0.90dL/g; 0.60 to 0.85 dL/g; 0.60 to 0.80 dL/g; 0.60 to 0.75 dL/g; 0.60 toless than 0.75 dL/g; 0.60 to 0.72 dL/g; 0.60 to 0.70 dL/g; 0.60 to lessthan 0.70 dL/g; 0.60 to 0.68 dL/g; 0.60 to less than 0.68 dL/g; 0.60 to0.65 dL/g; 0.65 to 1.2 dL/g; 0.65 to 1.1 dL/g; 0.65 to 1 dL/g; 0.65 toless than 1 dL/g; 0.65 to 0.98 dL/g; 0.65 to 0.95 dL/g; 0.65 to 0.90dL/g; 0.65 to 0.85 dL/g; 0.65 to 0.80 dL/g; 0.65 to 0.75 dL/g; 0.65 toless than 0.75 dL/g; 0.65 to 0.72 dL/g; 0.65 to 0.70 dL/g; 0.65 to lessthan 0.70 dL/g; 0.68 to 1.2 dL/g; 0.68 to 1.1 dL/g; 0.68 to I dL/g; 0.68to less than 1 dL/g; 0.68 to 0.98 dL/g; 0.68 to 0.95 dL/g; 0.68 to 0.90dL/g; 0.68 to 0.85 dL/g; 0.68 to 0.80 dL/g; 0.68 to 0.75 dL/g; 0.68 toless than 0.75 dL/g; 0.68 to 0.72 dL/g; greater than 0.76 dL/g to 1.2dL/g; greater than 0.76 dL/g to 1.1 dL/g; greater than 0.76 dL/g to IdL/g; greater than 0.76 dL/g to less than 1 dL/g; greater than 0.76 dL/gto 0.98 dL/g; greater than 0.76 dL/g to 0.95 dL/g; greater than 0.76dL/g to 0.90 dL/g; greater than 0.80 dL/g to 1.2 dL/g; greater than 0.80dL/g to 1.1 dL/g; greater than 0.80 dL/g to 1 dL/g; greater than 0.80dL/g to less than 1 dL/g; greater than 0.80 dL/g to 1.2 dL/g; greaterthan 0.80 dL/g to 0.98 dL/g; greater than 0.80 dL/g to 0.95 dL/g;greater than 0.80 dL/g to 0.90 dL/g.

It is contemplated that the polyesters useful in the invention canpossess at least one of the inherent viscosity ranges described hereinand at least one of the monomer ranges for the polyesters describedherein unless otherwise stated. It is also contemplated that thepolyester useful in the invention can possess at least one of the Tgranges described herein and at least one of the monomer ranges for thepolyesters described herein unless otherwise stated.

It is also contemplated that the polyesters useful in the invention canposses at least one of the Tg ranges described herein, at least one ofthe inherent viscosity ranges described herein, and at least one of themonomer ranges for the compositions described herein unless otherwisestated.

For the desired polyester, the molar ratio of cis/trans2,2,4,4-tetramethyl-1,3-cyclobutanediol can vary from the pure form ofeach or mixtures thereof. In certain embodiments, the molar percentagesfor cis and/or trans 2,2,4,4-tetramethyl-13-cyclobutanediol are greaterthan 50 mole % cis and less than 50 mole % trans; or greater than 55mole % cis and less than 45 mole % trans; or 30 to 70 mole % cis and 70to 30% trans; or 40 to 60 mole % cis and 60 to 40 mole % trans; or 50 to70 mole % trans and 50 to 30 mole % cis; or 50 to 70 mole % cis and 50to 30% trans or 60 to 70 mole % cis and 30 to 40 mole % trans; orgreater than 70 mole % cis and less than 30 mole % trans; wherein thetotal sum of the mole percentages for cis- andtrans-2,2,4,4-tetramethyl-1,3-cyclobutanediol is equal to 100 mole %.The molar ratio of cis/trans 1,4-cyclohexanedimethanol can vary withinthe range of 50/50 to 0/100, for example, between 40/60 to 20/80.

In certain embodiments, terephthalic acid, or an ester thereof, such as,for example, dimethyl terephthalate, or a mixture of terephthalic acidand an ester thereof, makes up most or all of the dicarboxylic acidcomponent used to form the polyesters useful in the invention. Incertain embodiments, terephthalic acid residues can make up a portion orall of the dicarboxylic acid component used to form the presentpolyester at a concentration of at least 70 mole %, such as at least 80mole %, at least 90 mole %, at least 95 mole %, at least 99 mole %, or100 mole %. In certain embodiments, polyesters with higher amounts ofterephthalic acid can be used in order to produce higher impact strengthproperties. For purposes of this disclosure, the terms “terephthalicacid” and “dimethyl terephthalate are used interchangeably herein. Inone embodiment, dimethyl terephthalate is part or all of thedicarboxylic acid component used to make the polyesters useful in thepresent invention. In all embodiments, ranges of from 70 to 100 mole %;or 80 to 100 mole %; or 90 to 100 mole %; or 99 to 100 mole %; or 100mole % terephthalic acid and/or dimethyl terephthalate and/or mixturesthereof may be used.

In addition to terephthalic acid residues, the dicarboxylic acidcomponent of the polyesters useful in the invention can comprise up to30 mole %, up to 20 mole %, up to 10 mole %, up to 5 mole %, or up to 1mole % of one or more modifying aromatic dicarboxylic acids. Yet anotherembodiment contains 0 mole % modifying aromatic dicarboxylic acids.Thus, if present, it is contemplated that the amount of one or moremodifying aromatic dicarboxylic acids can range from any of thesepreceding endpoint values including, for example, from 0.01 to 30 mole%, from 0.01 to 20 mole %, from 0.01 to 10 mole %, from 0.01 to 5 mole%, or from 0.01 to 1 mole % of one or more modifying aromaticdicarboxylic acids. In one embodiment, modifying aromatic dicarboxylicacids that may be used in the present invention include but are notlimited to those having up to 20 carbon atoms, and that can be linear,para-oriented, or symmetrical. Examples of modifying aromaticdicarboxylic acids which may be used in this invention include, but arenot limited to, isophthalic acid, 4,4′-biphenyldicarboxylic acid, 1,4-,1,5-, 2,6-, 2,7-naphthalenedicarboxylic acid, andtrans-4,4′-stilbenedicarboxylic acid, and esters thereof. In oneembodiment, isophthalic acid is the modifying aromatic dicarboxylicacid.

The carboxylic acid component of the polyesters useful in the inventioncan be further modified with up to 10 mole %, such as up to 5 mole % orup to 1 mole % of one or more aliphatic dicarboxylic acids containing2-16 carbon atoms, such as, for example, cyclohexanedicarboxylic,malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic anddodecanedioic dicarboxylic acids. Certain embodiments can also comprise0.01 or more mole %, such as 0.1 or more mole %, 1 or more mole %, 5 ormore mole %, or 10 or more mole % of one or more modifying aliphaticdicarboxylic acids. Yet another embodiment contains 0 mole % modifyingaliphatic dicarboxylic acids. Thus, if present, it is contemplated thatthe amount of one or more modifying aliphatic dicarboxylic acids canrange from any of these preceding endpoint values including, forexample, from 0.01 to 10 mole %, and from 0.1 to 10 mole %. The totalmole % of the dicarboxylic acid component is 100 mole %.

The modifying dicarboxylic acids of the invention can include indandicarboxylic acids, for example, indan-1,3-dicarboxylic acids and/orphenylindan dicarboxylic acids. In one embodiment, the dicarboxylic acidmay be chosen from at least one of1,2,3-trimethyl-3-phenylindan-4′,5-dicarboxylic acid and1,1,3-trimethyl-5-carboxy-3-(4-carboxyphenyl)indan dicarboxylic acid.For the purposes of this invention, any of the indan dicarboxylic acidsdescribed in United States Patent Application Publication No.2006/0004151A1 entitled “Copolymers Containing Indan Moieties and BlendsThereof” by Shaikh et al., assigned to General Electric Company may beused as at least one modifying dicarboxylic acid within the scope ofthis invention; United States Patent Application Publication No.2006/0004151A1 is incorporated herein by reference with respect to anyof the indan dicarboxylic acids described therein.

Esters of terephthalic acid and the other modifying dicarboxylic acidsor their corresponding esters and/or salts may be used instead of thedicarboxylic acids. Suitable examples of dicarboxylic acid estersinclude, but are not limited to, the dimethyl, diethyl, dipropyl,diisopropyl, dibutyl, and diphenyl esters. In one embodiment, the estersare chosen from at least one of the following: methyl, ethyl, propyl,isopropyl, and phenyl esters.

The cyclohexanedimethanol may be cis, trans, or a mixture thereof, forexample, a cis/trans ratio of 60:40 to 40:60 or a cis/trans ratio of70:30 to 30:70. In another embodiment, the trans-cyclohexanedimethanolcan be present in an amount of 60 to 80 mole % and thecis-cyclohexanedimethanol can be present in an amount of 20 to 40 mole %wherein the total ratio of cis and trans cyclohexanedimethanol is equalto 100 mole %. In particular embodiments, thetrans-cyclohexanedimethanol can be present in an amount of 60 mole % andthe cis-cyclohexanedimethanol can be present in an amount of 40 mole %.In particular embodiments, the trans-cyclohexanedimethanol can bepresent in an amount of 70 mole % and the cis-cyclohexanedimethanol canbe present in an amount of 30 mole %. Any of 1,1-, 1,2-, 1,3-,1,4-isomers of cyclohexanedimethanol or mixtures thereof may be presentin the glycol component of this invention. In one embodiment, thepolyesters useful in the invention comprise 1,4-cyclohexanedimethanol.In another embodiment, the polyesters useful in the invention comprise1,4-cyclohexanedimethanol and 1,3-cyclohexanedimethanol.

The glycol component of the polyester portion of the polyestercompositions useful in the invention can contain 25 mole % or less ofone or more modifying glycols which are not2,2,4,4-tetramethyl-1,3-cyclobutanediol or cyclohexanedimethanol; in oneembodiment, the polyesters useful in the invention can contain less than15 mole % of one or more modifying glycols. In another embodiment, thepolyesters useful in the invention can contain 10 mole % or less of oneor more modifying glycols. In another embodiment, the polyesters usefulin the invention can contain 5 mole % or less of one or more modifyingglycols. In another embodiment, the polyesters useful in the inventioncan contain 3 mole % or less of one or more modifying glycols. Inanother embodiment, the polyesters useful in the invention may contain 0mole % modifying glycols. Certain embodiments can also contain 0.01 ormore mole %, such as 0.1 or more mole %, I or more mole %, 5 or moremole %, or 10 or more mole % of one or more modifying glycols. Thus, ifpresent, it is contemplated that the amount of one or more modifyingglycols can range from any of these preceding endpoint values including,for example, from 0.01 to 15 mole % and from 0.1 to 10 mole %.

Modifying glycols useful in the polyesters useful in the invention referto diols other than 2,2,4,4,-tetramethyl-1,3-cyclobutanediol andcyclohexanedimethanol and may contain 2 to 16 carbon atoms. Examples ofsuitable modifying glycols include, but are not limited to, ethyleneglycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, neopentylglycol, 1,4 butanediol, 1,5-pentanediol, 1,6-hexanediol, p-xyleneglycol, polytetramethylene glycol, or mixtures thereof. In oneembodiment, the modifying glycol is ethylene glycol. In anotherembodiment, the modifying glycols include but are not limited to1,3-propanediol and/or 1,4-butanediol. In another embodiment, ethyleneglycol is excluded as a modifying diol. In another embodiment,1,3-propanediol and 1,4-butanediol are excluded as modifying diols. Inanother embodiment, 2,2-dimethyl-1,3-propanediol is excluded as amodifying diol. The polyesters and/or the polycarbonates useful in thepolyesters compositions of the invention can comprise from 0 to 10 molepercent, for example, from 0.01 to 5 mole percent, from 0.01 to 1 molepercent, from 0.05 to 5 mole percent, from 0.05 to 1 mole percent, orfrom 0.1 to 0.7 mole percent, or 0.1 to 0.5 mole percent, based thetotal mole percentages of either the diol or diacid residues;respectively, of one or more residues of a branching monomer, alsoreferred to herein as a branching agent, having 3 or more carboxylsubstituents, hydroxyl substituents, or a combination thereof. Incertain embodiments, the branching monomer or agent may be added priorto and/or during and/or after the polymerization of the polyester. Thepolyester(s) useful in the invention can thus be linear or branched. Thepolycarbonate can also be linear or branched. In certain embodiments,the branching monomer or agent may be added prior to and/or duringand/or after the polymerization of the polycarbonate.

Examples of branching monomers include, but are not limited to,multifunctional acids or multifunctional alcohols such as trimelliticacid, trimellitic anhydride, pyromellitic dianhydride,trimethylolpropane, glycerol, pentaerythritol, citric acid, tartaricacid, 3-hydroxyglutaric acid and the like. In one embodiment, thebranching monomer residues can comprise 0.1 to 0.7 mole percent of oneor more residues chosen from at least one of the following: trimelliticanhydride, pyromellitic dianhydride, glycerol, sorbitol,1,2,6-hexanetriol, pentaerythritol, trimethylolethane, and/or trimesicacid. The branching monomer may be added to the polyester reactionmixture or blended with the polyester in the form of a concentrate asdescribed, for example, in U.S. Pat. Nos. 5,654,347 and 5,696,176, whosedisclosure regarding branching monomers is incorporated herein byreference.

The glass transition temperature (Tg) of the polyesters useful in theinvention was determined using a TA DSC 2920 from Thermal AnalystInstrument at a scan rate of 20° C./min.

Because of the long crystallization half-times (e.g., greater than 5minutes) at 170° C. exhibited by certain polyesters useful in thepresent invention, it can be possible to produce articles, including butnot limited to, injection molded parts, injection blow molded articles,injection stretch blow molded articles, extruded film, extruded sheet,extrusion blow molded articles, extrusion stretch blow molded articles,and fibers. A thermoformable sheet is an example of an article ofmanufacture provided by this invention. The polyesters of the inventioncan be amorphous or semicrystalline. In one aspect, certain polyestersuseful in the invention can have relatively low crystallinity. Certainpolyesters useful in the invention can thus have a substantiallyamorphous morphology, meaning that the polyesters comprise substantiallyunordered regions of polymer.

In one embodiment, an “amorphous” polyester can have a crystallizationhalf-time of greater than 5 minutes at 170° C. or greater than 10minutes at 170° C. or greater than 50 minutes at 170° C. or greater than100 minutes at 170° C. In one embodiment, of the invention, thecrystallization half-times are greater than 1,000 minutes at 170° C. Inanother embodiment of the invention, the crystallization half-times ofthe polyesters useful in the invention are greater than 10,000 minutesat 170° C. The crystallization halftime of the polyesters, as usedherein, may be measured using methods well-known to persons of skill inthe art. For example, the crystallization half time of the polyester,t_(1/2), can be determined by measuring the light transmission of asample via a laser and photo detector as a function of time on atemperature controlled hot stage. This measurement can be done byexposing the polymers to a temperature, T_(max), and then cooling it tothe desired temperature. The sample can then be held at the desiredtemperature by a hot stage while transmission measurements were made asa function of time. Initially, the sample can be visually clear withhigh light transmission, and becomes opaque as the sample crystallizes.The crystallization half-time is the time at which the lighttransmission is halfway between the initial transmission and the finaltransmission. T_(max) is defined as the temperature required to melt thecrystalline domains of the sample (if crystalline domains are present).The sample can be heated to T_(max) to condition the sample prior tocrystallization half time measurement. The absolute T_(max) temperatureis different for each composition. For example PCT can be heated to sometemperature greater than 290° C. to melt the crystalline domains.

As shown in Table 1 and FIG. 1 of the Examples,2,2,4,4-tetramethyl-1,3-cyclobutanediol is more effective than othercomonomers such ethylene glycol and isophthalic acid at increasing thecrystallization half-time, i.e., the time required for a polymer toreach half of its maximum crystallinity. By decreasing thecrystallization rate of PCT, i.e. increasing the crystallizationhalf-time, amorphous articles based on modified —PCT may be fabricatedby methods known in the art such as extrusion, injection molding, andthe like. As shown in Table 1, these materials can exhibit higher glasstransition temperatures and lower densities than other modified PCTcopolyesters.

The polyesters of the invention can exhibit an improvement in toughnesscombined with processability for some of the embodiments of theinvention. For example, it is unexpected that lowering the inherentviscosity slightly of the polyesters useful in the invention results ina more processable melt viscosity while retaining good physicalproperties of the polyesters such as toughness and heat resistance.

Increasing the content of cyclohexanedimethanol in a copolyester basedon terephthalic acid, ethylene glycol, and cyclohexanedimethanol canimprove toughness can be determined by the brittle-to-ductile transitiontemperature in a notched Izod impact strength test as measured by ASTMD256. This toughness improvement, by lowering of the brittle-to-ductiletransition temperature with cyclohexanedimethanol, is believed to occurdue to the flexibility and conformational behavior ofcyclohexanedimethanol in the copolyester. Incorporating2,2,4,4-tetramethyl-1,3-cyclobutanediol into PCT is believed to improvetoughness, by lowering the brittle-to-ductile transition temperature, asshown in Table 2 and FIG. 2 of the Examples. This is unexpected giventhe rigidity of 2,2,4,4-tetramethyl-1,3-cyclobutanediol.

In one embodiment, the melt viscosity of the polyester(s) useful in theinvention is less than 30,000 poise as measured a 1 radian/second on arotary melt rheometer at 290° C. In another embodiment, the meltviscosity of the polyester(s) useful in the invention is less than20,000 poise as measured a 1 radian/second on a rotary melt rheometer at290° C.

In one embodiment, the melt viscosity of the polyester(s) useful in theinvention is less than 15,000 poise as measured at 1 radian/second(rad/sec) on a rotary melt rheometer at 290° C. In one embodiment, themelt viscosity of the polyester(s) useful in the invention is less than10,000 poise as measured at I radian/second (rad/sec) on a rotary meltrheometer at 290° C. In another embodiment, the melt viscosity of thepolyester(s) useful in the invention is less than 6,000 poise asmeasured at 1 radian/second on a rotary melt rheometer at 290° C.Viscosity at rad/sec is related to processability. Typical polymers haveviscosities of less than 10,000 poise as measured at I radian/secondwhen measured at their processing temperature. Polyesters are typicallynot processed above 290° C. Polycarbonate is typically processed at 290°C. The viscosity at 1 rad/sec of a typical 12 melt flow ratepolycarbonate is 7000 poise at 290° C.

In one embodiment, polyesters of this invention exhibit superior notchedtoughness in thick sections. Notched Izod impact strength, as describedin ASTM D256, is a common method of measuring toughness. The presentpolyesters useful in this invention can possess one or more of thefollowing properties. In one embodiment, the polyesters useful in theinvention exhibit a impact strength of at least 150 J/m (3 ft-lb/in) at23° C. with a 10-mil notch in a 3.2 mm (⅛-inch) thick bar determinedaccording to ASTM D256; in one embodiment, the polyesters useful in theinvention exhibit a notched Izod impact strength of at least (400 J/m)7.5 ft-lb/in at 23° C. with a 10-mil notch in a 3.2 mm (⅛-inch) thickbar determined according to ASTM D256; in one embodiment, the polyestersuseful in the invention exhibit a notched Izod impact strength of atleast 1000 J/m (18 ft-lb/in) at 23° C. with a 10-mil notch in a 3.2 mm(⅛-inch) thick bar determined according to ASTM D256. In one embodiment,the polyesters useful in the invention exhibit a notched Izod impactstrength of at least 150 J/m (3 ft-lb/in) at 23° C. with a 10-mil notchin a 6.4 mm (¼-inch) thick bar determined according to ASTM D256; in oneembodiment, the polyesters useful in the invention exhibit a notchedIzod impact strength of at least (400 J/m) 7.5 ft-lb/in at 23° C. with a10-mil notch in a 6.4 mm (¼-inch) thick bar determined according to ASTMD256; in one embodiment, the polyesters useful in the invention exhibita notched Izod impact strength of at least 1000 J/m (18 ft-lb/in) at 23°C. with a 10-mil notch in a 6.4 mm (¼-inch) thick bar determinedaccording to ASTM D256.

In another embodiment, certain polyesters useful in the invention canexhibit an increase in notched Izod impact strength when measured at 0°C. of at least 3% or at least 5% or at least 10% or at least 15% ascompared to the notched Izod impact strength when measured at −5° C.with a 10-mil notch in a ⅛-inch thick bar determined according to ASTMD256. In addition, certain other polyesters can also exhibit a retentionof notched Izod impact strength within plus or minus 5% when measured at0° C. through 30° C. with a 10-mil notch in a ⅛-inch thick bardetermined according to ASTM D256.

In yet another embodiment, certain polyesters useful in the inventioncan exhibit a retention in notched Izod impact strength with a loss ofno more than 70% when measured at 23° C. with a 10-mil notch in a ¼-inchthick bar determined according to ASTM D256 as compared to notched Izodimpact strength for the same polyester when measured at the sametemperature with a 10-mil notch in a ⅛-inch thick bar determinedaccording to ASTM D256.

In one embodiment, the polyesters useful in the invention can exhibit aductile-to-brittle transition temperature of less than 0° C. based on a10-mil notch in a ⅛-inch thick bar as defined by ASTM D256.

In one embodiment, the polyesters useful in this invention can bevisually clear. The term “visually clear” is defined herein as anappreciable absence of cloudiness, haziness, and/or muddiness, wheninspected visually. In another embodiment, when the polyesters areblended with polycarbonate, including, but not limited to, bisphenol Apolycarbonates, the blends can be visually clear.

The present polyesters possess one or more of the following properties.In other embodiments, the polyesters useful in the invention may have ayellowness index (ASTM D-1925) of less than 50 or less than 20.

In one embodiment, the polyesters useful in the invention and/or thepolyester compositions of the invention, with or without toners, canhave color values L*, a* and b* which can be determined using a HunterLab Ultrascan Spectra Colorimeter manufactured by Hunter Associates LabInc., Reston, Va. The color determinations are averages of valuesmeasured on either pellets of the polyesters or plaques or other itemsinjection molded or extruded from them. They are determined by theL*a*b* color system of the CIE (International Commission onIllumination) (translated), wherein L* represents the lightnesscoordinate, a* represents the red/green coordinate, and b* representsthe yellow/blue coordinate. In certain embodiments, the b* values forthe polyesters useful in the invention can be from −10 to less than 10and the L* values can be from 50 to 90. In other embodiments, the b*values for the polyesters useful in the invention can be present in oneof the following ranges: −10 to 9; −10 to 8; −10 to 7; −10 to 6; −10 to5; −10 to 4; −10 to 3; −10 to 2; from −5 to 9; −5 to 8; −5 to 7; −5 to6; −5 to 5; −5 to 4; −5 to 3; −5 to 2; 0 to 9; 0 to 8; 0 to 7; 0 to 6; 0to 5; 0 to 4; 0 to 3; 0 to 2; 1 to 10; 1 to 9; 1 to 8; 1 to 7; 1 to 6; 1to 5; 1 to 4; 1 to 3; and 1 to 2. In other embodiments, the L* value forthe polyesters useful in the invention can be present in one of thefollowing ranges: 50 to 60; 50 to 70; 50 to 80; 50 to 90; 60 to 70; 60to 80; 60 to 90; 70 to 80; 79 to 90.

In one embodiment, the polyesters useful in the invention can exhibit atleast one of the following densities: a density of less than 1.3 g/ml at23° C.; a density of less than 1.2 g/ml at 23° C.; a density of lessthan 1.18 g/ml at 23° C.; a density of 0.70 to 1.2 g/ml at 23° C.; adensity of 0.70 to 1.3 g/ml at 23° C.; a density of 0.70 to less than1.2 g/ml at 23° C.; a density of 0.75 to 1.2 at 23° C.; a density of0.75 g/ml to less than 1.2 at 23° C.; a density of 0.80 g/ml to 1.2 at23° C.; a density of 0.80 to less than 1.2 g/ml at 23° C.; a density of0.90 to 1.2 g/ml at 23° C.; a density of 1.0 to 1.2 g/ml at 23° C.; adensity of 1.0 to 1.3 g/ml at 23° C. a density of 1.1 to 1.2 g/ml at 23°C.; a density of 1.13 to 1.3 g/ml at 23° C. a density of 1.13 to 1.2g/ml at 23° C.; a density of 0.80 to 1.18 at 23° C.; a density of 0.80to less than 1.18 g/ml at 23° C.; a density of 1.0 to less than 1.18g/ml at 23° C.; a density of 1.1 to less than 1.18 g/ml at 23° C.

In some embodiments, use of the polyester compositions useful in theinvention minimizes and/or eliminates the drying step prior to meltprocessing and/or thermoforming.

Although the polyesters useful in this invention can have any moisturecontent, in one embodiment, they may have a moisture content of 0.02 to1.0 weight percent of the total weight of the polyester prior to meltprocessing.

In certain embodiments, the polyesters are dried by conventional methodsfor less than 2 hours at 60° C. to 100° C. prior to melt processing.

The polyesters and/or polyester compositions and/or processes eitheruseful in the invention or of the invention can comprise at least onethermal stabilizer.

Thermal stabilizers are compounds that stabilize polyesters duringpolyester manufacture and/or post polymerization, including but notlimited to phosphorous compounds including but not limited to phosphoricacid, phosphorous acid, phosphonic acid, phosphinic acid, phosphonousacid, and various esters and salts thereof. These can be present in thepolyester compositions useful in the invention. The esters can be alkyl,branched alkyl, substituted alkyl, difunctional alkyl, alkyl ethers,aryl, and substituted aryl. In one embodiment, the number of estergroups present in the particular phosphorous compound can vary from zeroup to the maximum allowable based on the number of hydroxyl groupspresent on the thermal stabilizer used.

The term “thermal stabilizer” is intended to include the reactionproduct(s) thereof. The term “reaction product” as used in connectionwith the thermal stabilizers of the invention refers to any product of apolycondensation or esterification reaction between the thermalstabilizer and any of the monomers used in making the polyester as wellas the product of a polycondensation or esterification reaction betweenthe catalyst and any other type of additive.

In one embodiment, the thermal stabilizer(s) useful in the invention canbe an organic compound such as, for example, a phosphorus acid estercontaining halogenated or non-halogenated organic substituents. Thethermal stabilizer can comprise a wide range of phosphorus compoundswell-known in the art such as, for example, phosphines, phosphites,phosphinites, phosphonites, phosphinates, phosphonates, phosphineoxides, and phosphates. Examples of thermal stabilizers include tributylphosphate, triethyl phosphate, tri-butoxyethyl phosphate, t-butylphenyldiphenyl phosphate, 2-ethylhexyl diphenyl phosphate, ethyl dimethylphosphate, isodecyl diphenyl phosphate, trilauryl phosphate, triphenylphosphate, tricresyl phosphate, trixylenyl phosphate, t-butylphenyldiphenylphosphate, resorcinol bis(diphenyl phosphate), tribenzylphosphate, phenyl ethyl phosphate, trimethyl thionophosphate, phenylethyl thionophosphate, dimethyl methylphosphonate, diethylmethylphosphonate, diethyl pentylphosphonate, dilaurylmethylphosphonate, diphenyl methylphosphonate, dibenzylmethylphosphonate, diphenyl cresylphosphonate, dimethylcresylphosphonate, dimethyl methylthionophosphonate, phenyldiphenylphosphinate, benzyl diphenylphosphinate, methyldiphenylphosphinate, trimethyl phosphine oxide, triphenyl phosphineoxide, tribenzyl phosphine oxide, 4-methyl diphenyl phosphine oxide,triethyl phosphite, tributyl phosphite, trilauryl phosphite, triphenylphosphite, tribenzyl phosphite, phenyl diethyl phosphite, phenyldimethyl phosphite, benzyl dimethyl phosphite, dimethylmethylphosphonite, diethyl pentylphosphonite, diphenylmethylphosphonite, dibenzyl methylphosphonite, dimethylcresylphosphonite, methyl dimethylphosphinite, methyldiethylphosphinite, phenyl diphenylphosphinite, methyldiphenylphosphinite, benzyl diphenylphosphinite, triphenyl phosphine,tribenzyl phosphine, and methyl diphenyl phosphine. In one embodiment,triphenyl phosphine oxide is excluded as a thermal stabilizer in theprocess(es) of making the polyesters useful in the invention and in thepolyester composition(s) of the invention.

In one embodiment, thermal stabilizers useful in the invention can beany of the previously described phosphorus-based acids wherein one ormore of the hydrogen atoms of the acid compound (bonded to either oxygenor phosphorus atoms) are replaced with alkyl, branched alkyl,substituted alkyl, alkyl ethers, substituted alkyl ethers, alkyl-aryl,alkyl-substituted aryl, aryl, substituted aryl, and mixtures thereof. Inanother embodiment, thermal stabilizers useful in the invention, includebut are not limited to, the above described compounds wherein at leastone of the hydrogen atoms bonded to an oxygen atom of the compound isreplaced with a metallic ion or an ammonium ion.

The esters can contain alkyl, branched alkyl, substituted alkyl, alkylethers, aryl, and/or substituted aryl groups. The esters can also haveat least one alkyl group and at least one aryl group. The number ofester groups present in the particular phosphorus compound can vary fromzero up to the maximum allowable based on the number of hydroxyl groupspresent on the phosphorus compound used. For example, an alkyl phosphateester can include one or more of the mono-, di-, and tri alkyl phosphateesters; an aryl phosphate ester includes one or more of the mono-, di-,and tri aryl phosphate esters; and an alkyl phosphate ester and/or anaryl phosphate ester also include, but are not limited to, mixed alkylaryl phosphate esters having at least one alkyl and one aryl group.

In one embodiment, the thermal stabilizers useful in the inventioninclude but are not limited to alkyl, aryl or mixed alkyl aryl esters orpartial esters of phosphoric acid, phosphorus acid, phosphinic acid,phosphonic acid, or phosphonous acid. The alkyl or aryl groups cancontain one or more substituents.

In one aspect, the phosphorus compounds useful in the invention compriseat least one thermal stabilizer chosen from at least one of substitutedor unsubstituted alkyl phosphate esters, substituted or unsubstitutedaryl phosphate esters, substituted or unsubstituted mixed alkyl arylphosphate esters, diphosphites, salts of phosphoric acid, phosphineoxides, and mixed aryl alkyl phosphites, reaction products thereof, andmixtures thereof. The phosphate esters include esters in which thephosphoric acid is fully esterified or only partially esterified.

In one embodiment, for example, the thermal stabilizers useful in theinvention can include at least one phosphate ester.

In one aspect, the phosphorus compounds useful in the invention compriseat least one thermal stabilizer chosen from at least one of substitutedor unsubstituted alkyl phosphate esters, substituted or unsubstitutedaryl phosphate esters, mixed substituted or unsubstituted alkyl arylphosphate esters, reaction products thereof, and mixtures thereof. Thephosphate esters include esters in which the phosphoric acid is fullyesterified or only partially esterified.

In one embodiment, for example, the thermal stabilizers useful in theinvention can include at least one phosphate ester.

In another embodiment, the phosphate esters useful in the invention caninclude but are not limited to alkyl phosphate esters, aryl phosphateesters, mixed alkyl aryl phosphate esters, and/or mixtures thereof.

In certain embodiments, the phosphate esters useful in the invention arethose where the groups on the phosphate ester include are alkyl,alkoxy-alkyl, phenyl, or substituted phenyl groups. These phosphateesters are generally referred to herein as alkyl and/or aryl phosphateesters. Certain preferred embodiments include trialkyl phosphates,triaryl phosphates, alkyl diaryl phosphates, dialkyl aryl phosphates,and mixtures of such phosphates, wherein the alkyl groups are preferablythose containing from 2 to 12 carbon atoms, and the aryl groups arepreferably phenyl.

Representative alkyl and branched alkyl groups are preferably thosecontaining from 1-12 carbon atoms, including, but not limited to, ethyl,propyl, isopropyl, butyl, hexyl, cyclohexyl, 2-ethylhexyl, octyl, decyland dodecyl. Substituted alkyl groups include, but are not limited to,those containing at least one of carboxylic acid groups and estersthereof, hydroxyl groups, amino groups, keto groups, and the like.

Representative of alkyl-aryl and substituted alkyl-aryl groups are thosewherein the alkyl portion contains from 1-12 carbon atoms, and the arylgroup is phenyl or substituted phenyl wherein groups such as alkyl,branched alkyl, aryl, hydroxyl, and the like are substituted forhydrogen at any carbon position on the phenyl ring. Preferred arylgroups include phenyl or substituted phenyl wherein groups such asalkyl, branched alkyl, aryl, hydroxyl and the like are substituted forhydrogen at any position on the phenyl ring.

In one embodiment, the phosphate esters useful as thermal stabilizers inthe invention include but are not limited to dibutylphenyl phosphate,triphenyl phosphate, tricresyl phosphate, tributyl phosphate,tri-2-ethylhexyl phosphate, trioctyl phosphate, and/or mixtures thereof,including particularly mixtures of tributyl phosphate and tricresylphosphate, and mixtures of isocetyl diphenyl phosphate and 2-ethylhexyldiphenyl phosphate.

In one embodiment, the phosphate esters useful as thermal stabilizers inthe invention include but are not limited to, at least one of thefollowing: trialkyl phosphates, triaryl phosphates, alkyl diarylphosphates, and mixed alkyl aryl phosphates.

In one embodiment, the phosphate esters useful as thermal stabilizers inthe invention include but are not limited to, at least one of thefollowing: triaryl phosphates, alkyl diaryl phosphates, and mixed alkylaryl phosphates.

In one embodiment, the phosphate esters useful as thermal stabilizers inthe invention include but are not limited to, at least one of thefollowing: triaryl phosphates and mixed alkyl aryl phosphates. In oneembodiment, at least one thermal stabilizer comprises, but is notlimited to, triaryl phosphates, such as, for example, triphenylphosphate. In one embodiment, at least one one thermal stabilizercomprises, but is not limited to Merpol A.

In one embodiment, at least one thermal stabilizer useful in theinvention comprises, but is not limited to, triaryl phosphates, such as,for example, triphenyl phosphate. In one embodiment, at least one onethermal stabilizer comprises, but is not limited to Merpol A. In oneembodiment, at least one thermal stabilizer useful in the inventioncomprises, but is not limited to, at least one of triphenyl phosphateand Merpol A. Merpol A is a phosphate ester commercially available fromStepan Chemical Co and/or E.I. duPont de Nemours & Co. The CAS Registrynumber for Merpol A is believed to be CAS Registry # 37208-27-8.

In one embodiment, the polyester compositions and/or processes of theinvention may comprise 2-ethylhexyl diphenyl phosphate.

In one embodiment, the polyester compositions and/or processes of theinvention may comprise 2-ethylhexyl diphenyl phosphate.

In one embodiment, the phosphorus compounds useful in the inventioncomprise, but are not limited to, at least one diphosphite.

In one embodiment, the phosphorus compounds useful in the inventioncomprise, but are not limited to, at least one diphosphite whichcontains a 2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane structure,such as, for example, Weston 619 (GE Specialty Chemicals, CAS#3806-34-6) and/or Doverphos S-9228 (Dover Chemicals, CAS# 154862-43-8).

In one embodiment, the phosphorus compounds useful in the inventioncomprise at least one phosphine oxide, such as, for example,triphenylphosphine oxide.

In one embodiment, the phosphorus compounds useful in the inventioncomprise at least one mixed alkyl aryl phosphites, such as, for example,bis(2,4-dicumylphenyl)pentaerythritol diphosphite also known asDoverphos S-9228 (Dover Chemicals, CAS# 154862-43-8).

In one embodiment, any of processes described herein for making thepolyester compositions and/or polyesters comprise at least one of thephosphorus compounds described herein.

In one embodiment, any of processes described herein for making any ofthe polyester compositions and/or polyesters can comprise at least onediphosphite.

In one embodiment, any of the processes described herein for making anyof the polyester compositions and/or polyesters can comprise, at leastone diphosphite which contains a2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane structure, such as,for example, Weston 619 (GE Specialty Chemicals, CAS# 3806-34-6) and/orDoverphos S-9228 (Dover Chemicals, CAS# 154862-43-8).

In one embodiment, any of the processes described herein for making anyof the polyester compositions and/or polyesters can comprise at leastone phosphine oxide, such as, for example, triphenylphosphine oxide.

In one embodiment, any of the processes described herein for making anyof the polyester compositions and/or polyesters can comprise at leastone mixed alkyl aryl phosphites, such as, for example,bis(2,4-dicumylphenyl)pentaerythritol diphosphite also known asDoverphos S-9228 (Dover Chemicals, CAS# 154862-43-8).

When phosphorus is added to the polyesters and/or polyester compositionsand/or process of making the polyesters of the invention, it is added inthe form of a phosphorus compound as described herein, for example, atleast one phosphate ester, at least one diphosphite, at least one saltof phosphoric acid. The amount of phosphorus compound(s), (for example,at least one diphosphite), is added to the polyesters of the inventionand/or polyester compositions of the invention and/or processes of theinvention can be measured in the form of phosphorus atoms present in thefinal polyester, for example, by weight measured in ppm.

Amounts of thermal stabilizer added during polymerization or postmanufacturing can include but are not limited to: 1 to 5000 ppm; 1 to1000 ppm, 1 to 900 ppm, 1 to 800 ppm, 1 to 700 ppm. 1 to 600 ppm, 1 to500 ppm, 1 to 400 ppm, 1 to 350 ppm, 1 to 300 ppm, 1 to 250 ppm, 1 to200 ppm, 1 to 150 ppm, 1 to 100 ppm; 10 to 5000 ppm; 10 to 1000 ppm, 10to 900 ppm, 10 to 800 ppm, 10 to 700 ppm. 10 to 600 ppm, 10 to 500 ppm,10 to 400 ppm, 10 to 350 ppm, 10 to 300 ppm, 10 to 250 ppm, 10 to 200ppm, 10 to 150 ppm, 10 to 100 ppm; based on the total weight of thepolyester composition.

In one embodiment, amounts of the phosphorus compound (for example,diphosphite, phosphate ester, etc.) of the invention added duringpolymerization are chosen from the following: 1 to 5000 ppm; 1 to 1000ppm, 1 to 900 ppm, 1 to 800 ppm, 1 to 700 ppm. 1 to 600 ppm, 1 to 500ppm, 1 to 400 ppm, 1 to 350 ppm, 1 to 300 ppm, 1 to 250 ppm, 1 to 200ppm, 1 to 150 ppm, 1 to 100 ppm; 1 to 60 ppm; 2 to 5000 ppm; 2 to 1000ppm, 2 to 900 ppm, 2 to 800 ppm, 2 to 700 ppm. 2 to 600 ppm, 2 to 500ppm, 2 to 400 ppm, 2 to 350 ppm, 2 to 300 ppm, 2 to 250 ppm, 2 to 200ppm, 2 to 150 ppm, 2 to 100 ppm; 2 to 60 ppm; 2 to 20 ppm, 3 to 5000ppm; 3 to 1000 ppm, 3 to 900 ppm, 3 to 800 ppm, 3 to 700 ppm. 3 to 600ppm, 3 to 500 ppm, 3 to 400 ppm, 3 to 350 ppm, 3 to 300 ppm, 3 to 250ppm, 3 to 200 ppm, 3 to 150 ppm, 3 to 100 ppm; 3 to 60 ppm; 3 to 20 ppm,4 to 5000 ppm; 4 to 1000 ppm, 4 to 900 ppm, 4 to 800 ppm, 4 to 700 ppm,4 to 600 ppm, 4 to 500 ppm, 4 to 400 ppm, 4 to 350 ppm, 4 to 300 ppm, 4to 250 ppm, 4 to 200 ppm, 4 to 150 ppm, 4 to 100 ppm; 4 to 60 ppm; 4 to20 ppm, 5 to 5000 ppm; 5 to 1000 ppm, 5 to 900 ppm, 5 to 800 ppm, 5 to700 ppm, 5 to 600 ppm, 5 to 500 ppm, 5 to 400 ppm, 5 to 350 ppm, 5 to300 ppm, 5 to 250 ppm, 5 to 200 ppm, 5 to 150 ppm, 5 to 100 ppm; 5 to 60ppm; 5 to 20 ppm, 6 to 5000 ppm; 6 to 1000 ppm, 6 to 900 ppm, 6 to 800ppm, 6 to 700 ppm, 6 to 600 ppm, 6 to 500 ppm, 6 to 400 ppm, 6 to 350ppm, 6 to 300 ppm, 6 to 250 ppm, 6 to 200 ppm, 6 to 150 ppm, 6 to 100ppm; 6 to 60 ppm; 6 to 20 ppm, 7 to 5000 ppm; 7 to 1000 ppm, 7 to 900ppm, 7 to 800 ppm, 7 to 700 ppm, 7 to 600 ppm, 7 to 500 ppm, 7 to 400ppm, 7 to 350 ppm, 7 to 300 ppm, 7 to 250 ppm, 7 to 200 ppm, 7 to 150ppm, 7 to 100 ppm; 7 to 60 ppm; 7 to 20 ppm, 8 to 5000 ppm; 8 to 1000ppm, 8 to 900 ppm, 8 to 800 ppm, 8 to 700 ppm, 8 to 600 ppm, 8 to 500ppm, 8 to 400 ppm, 8 to 350 ppm, 8 to 300 ppm, 8 to 250 ppm, 8 to 200ppm, 8 to 150 ppm, 8 to 100 ppm; 8 to 60 ppm; 8 to 20 ppm, 9 to 5000ppm; 9 to 1000 ppm, 9 to 900 ppm, 9 to 800 ppm, 9 to 700 ppm, 9 to 600ppm, 9 to 500 ppm, 9 to 400 ppm, 9 to 350 ppm, 9 to 300 ppm, 9 to 250ppm, 9 to 200 ppm, 9 to 150 ppm, 9 to 100 ppm; 9 to 60 ppm; 9 to 20 ppm,10 to 5000 ppm; 10 to 1000 ppm, 10 to 900 ppm, 10 to 800 ppm, 10 to 700ppm. 10 to 600 ppm, 10 to 500 ppm, 10 to 400 ppm, 10 to 350 ppm, 10 to300 ppm, 10 to 250 ppm, 10 to 200 ppm, 10 to 150 ppm, 10 to 100 ppm, 10to 60 ppm, 10 to 20 ppm, 50 to 5000 ppm, 50 to 1000 ppm, 50 to 900 ppm,50 to 800 ppm, 50 to 700 ppm, 50 to 600 ppm, 50 to 500 ppm, 50 to 400ppm, 50 to 350 ppm, 50 to 300 ppm, 50 to 250 ppm, 50 to 200 ppm, 50 to150 ppm, 50 to 100 ppm; 50 to 80 ppm, 100 to 5000 ppm, 100 to 1000 ppm,100 to 900 ppm, 100 to 800 ppm, 100 to 700 ppm, 100 to 600 ppm, 100 to500 ppm, 100 to 400 ppm, 100 to 350 ppm, 100 to 300 ppm, 100 to 250 ppm,100 to 200 ppm, 100 to 150 ppm; 150 to 5000 ppm, 150 to 1000 ppm, 150 to900 ppm, 150 to 800 ppm, 150 to 700 ppm, 150 to 600 ppm, 150 to 500 ppm,150 to 400 ppm, 150 to 350 ppm, 150 to 300 ppm, 150 to 250 ppm, 150 to200 ppm, 200 to 5000 ppm, 200 to 1000 ppm, 200 to 900 ppm, 200 to 800ppm, 200 to 700 ppm, 200 to 600 ppm, 200 to 500 ppm, 200 to 400 ppm, 200to 350 ppm, 200 to 300 ppm, 200 to 250 ppm, 250 to 5000 ppm, 250 to 1000ppm, 250 to 900 ppm, 250 to 800 ppm, 250 to 700 ppm, 250 to 600 ppm, 250to 500 ppm, 250 to 400 ppm, 250 to 350 ppm, 250 to 300 ppm, 500 to 5000ppm, 300 to 1000 ppm, 300 to 900 ppm, 300 to 800 ppm, 300 to 700 ppm,300 to 600 ppm, 300 to 500 ppm, 300 to 400 ppm, 300 to 350 ppm, 350 to5000 ppm, 350 to 1000 ppm, 350 to 900 ppm, 350 to 800 ppm, 350 to 700ppm, 350 to 600 ppm, 350 to 500 ppm, 350 to 400 ppm; based on the totalweight of the polyester composition and as measured in the form ofphosphorus atoms in the final polyester.

Suitable catalysts for use in the processes of the invention to make thepolyesters useful in the invention include at least one tin compound.The polyester compositions of the invention may also comprise at leastone of the tin compounds useful in the processes of the invention. Othercatalysts could possibly be used in the invention in combination withthe at least one tin compound Other catalysts may include, but are notlimited to, those based on titanium, gallium, zinc, antimony, cobalt,manganese, magnesium, germanium, lithium, aluminum compounds, and analuminum compound with lithium hydroxide or sodium hydroxide. In oneembodiment, the catalyst can be a combination of at least one tincompound and at least one titanium compound.

Catalyst amounts can range from 10 ppm to 20,000 ppm or 10 to 10,000ppm, or 10 to 5000 ppm or 10 to 1000 ppm or 10 to 500 ppm, or 10 to 300ppm or 10 to 250 ppm based on the catalyst metal and based on the weightof the final polymer. The process can be carried out in either a batchor continuous process. In one embodiment, the catalyst is a tincompound. In one embodiment, the catalyst is solely a tin compound. Inone embodiment, the tin compound can be used in either theesterification reaction or the polycondensation reaction or bothreactions. In another embodiment, the catalyst is solely a tin compoundused in the esterification reaction. Generally, in one embodiment, thetin compound catalyst is used in amounts of from about 0.005% to about0.2% based on the weight of the dicarboxylic acid or dicarboxylic acidester. Generally, in one embodiment, less than about 700 ppm elementaltin based on polyester weight should be present as residue in thepolyester based on the total weight of the polyester.

When tin is added to the polyesters and/or polyester compositions and/orprocess of making the polyesters of the invention, it is added to theprocess of making the polyester in the form of a tin compound. Theamount of the tin compound added to the polyesters of the inventionand/or polyester compositions of the invention and/or processes of theinvention can be measured in the form of tin atoms present in the finalpolyester, for example, by weight measured in ppm.

In another embodiment, the catalyst is solely a tin compound used in theesterification reaction in the amount of 10 ppm to 20,000 ppm or 10 to10,000 ppm, or 10 to 5000 ppm or 10 to 4500 ppm or 10 to 4000 ppm or 10to 3500 ppm or 10 to 3000 ppm or 10 to 2500 ppm or 10 to 2000 ppm or or10 to 1500 ppm or 10 to 1000 ppm or 10 to 500 ppm, or 10 to 300 ppm or10 to 250 ppm or 15 ppm to 20,000 ppm or 15 to 10,000 ppm, or 15 to 5000ppm or or 15 to 4500 ppm or 15 to 4000 ppm or 15 to 3500 ppm or 15 to3000 ppm or 15 to 2500 ppm or 15 to 2000 ppm or or 15 to 1500 ppm or 15to 1000 ppm or 15 to 500 ppm or 15 to 400 ppm or 15 to 300 ppm or 15 to250 ppm or 20 ppm to 20,000 ppm or 20 to 10,000 ppm, or 20 to 5000 ppmor or 20 to 4500 ppm or 20 to 4000 ppm or 20 to 3500 ppm or 20 to 3000ppm or 20 to 2500 ppm or 20 to 2000 ppm or or 20 to 1500 ppm or 20 to1000 ppm or 20 to 500 ppm, or 20 to 300 ppm or 20 to 250 ppm 25 ppm to20,000 ppm or 25 to 10,000 ppm, or 25 to 5000 ppm or or 25 to 4500 ppmor 25 to 4000 ppm or 25 to 3500 ppm or 25 to 3000 ppm or 25 to 2500 ppmor 25 to 2000 ppm or or 25 to 1500 ppm or 25 to 1000 ppm or 25 to 500ppm, or 25 to 400 ppm, or 25 to 300 ppm or 25 to 250 ppm or 30 ppm to20,000 ppm or 30 to 10,000 ppm, or 30 to 5000 ppm or 30 to 4500 ppm or30 to 4000 ppm or 30 to 3500 ppm or 30 to 3000 ppm or 30 to 2500 ppm or30 to 2000 ppm or or 30 to 1500 ppm pr 30 to 1000 ppm or 30 to 500 ppm,or 30 to 300 ppm or 30 to 250 ppm or 35 ppm to 20,000 ppm or 35 to10,000 ppm, or 35 to 5000 ppm or 35 to 4500 ppm or 35 to 4000 ppm or 35to 3500 ppm or 35 to 3000 ppm or 35 to 2500 ppm or 35 to 2000 ppm or or35 to 1500 ppm or 35 to 1000 ppm or 35 to 500 ppm, or 35 to 300 ppm or35 to 250 ppm or 40 ppm to 20,000 ppm or 40 to 10,000 ppm, or 40 to 5000ppm or or 40 to 4500 ppm or 40 to 4000 ppm or 40 to 3500 ppm or 40 to3000 ppm or 40 to 2500 ppm or 40 to 2000 ppm or or 40 to 1500 ppm or 40to 1000 ppm or 40 to 500 ppm, or 40 to 300 ppm or 40 to 250 ppm or 40 to200 ppm or 45 ppm to 20,000 ppm or 45 to 10,000 ppm, or 45 to 5000 ppmor 45 to 4500 ppm or 45 to 4000 ppm or 45 to 3500 ppm or 45 to 3000 ppmor 45 to 2500 ppm or 45 to 2000 ppm or 45 to 1500 ppm or 45 to 1000 ppmor 45 to 500 ppm, or 45 to 300 ppm or 45 to 250 ppm or 50 ppm to 20,000ppm or 50 to 10,000 ppm, or 50 to 5000 ppm or 50 to 4500 ppm or 50 to4000 ppm or 50 to 3500 ppm or 50 to 3000 ppm or 50 to 2500 ppm or 50 to2000 ppm or or 50 to 1500 ppm or 50 to 1000 ppm or 50 to 500 ppm, or 50to 300 ppm or 50 to 250 ppm or 50 to 200 ppm or 50 to 150 ppm 50 to 125ppm, based on the weight of the final polyester, as measured in the formof tin atoms in the final polyester.

In another embodiment, the polyesters of the invention can be preparedusing at least one tin compound as catalyst. For example, see U.S. Pat.No. 2,720,507, where the portion concerning tin catalysts isincorporated herein by reference. These catalysts are tin compoundscontaining at least one organic radical. These catalysts includecompounds of both divalent or tetravalent tin which have the generalformulas set forth below:

M₂(Sn(OR)₄)  A.

MH(Sn(OR)₄)  B.

M′(Sn(OR)₄)  C.

M′(HSn(OR)₄)₂  D.

M₂(Sn(OR)₆)  E.

MH(Sn(OR)₆)  F.

M′(Sn(OR)₆)  G.

M′(HSn(OR)₆)₂  H.

Sn(OR)₂  I.

Sn(OR)₄  J.

SnR′₂  K.

SnR′₄  L.

R′₂SnO  M.

wherein M is an alkali metal, e.g. lithium, sodium, or potassium, M′ isan alkaline earth metal such as Mg, Ca or Sr, each R represents an alkylradical containing from 1 to 8 carbon atoms, each R′ radical representsa substituent selected from those consisting of alkyl radicalscontaining from 1 to 8 carbon atoms (i.e. R radicals) and aryl radicalsof the benzene series containing from 6 to 9 carbon atoms (e.g. phenyl,tolyl, benzyl, phenylethyl, etc., radicals), and Ac represents an acylradical derived from an organic acid containing from 2 to 18 carbonatoms (e.g. acetyl, butyryl, lauroyl, benzoyl, stearoyl, etc.).

The novel bimetallic alkoxide catalysts can be made as described byMeerwein, Ann. 476, 113 (1929). As shown by Meerwein, these catalystsare not merely mixtures of the two metallic alkoxides. They are definitecompounds having a salt-like structure. These are the compounds depictedabove by the Formulas A through H. Those not specifically described byMeerwein can be prepared by procedures analogous to the working examplesand methods set forth by Meerwein.

The other tin compounds can also be made by various methods such asthose described in the following literature:

For the preparation of diaryl tin dihalides (Formula P) see Ber. 62, 996(1929); J. Am. Chem. Soc. 49,1369 (1927). For the preparation of dialkyltin dihalides (Formula P) see J. Am. Chem. Soc. 47, 2568 (1925); C.A.41, 90 (1947). For the preparation of diaryl tin oxides (Formula M) seeJ. Am. Chem. Soc. 48,1054 (1926). For the preparation of tetraaryl tincompounds (Formula K) see C.A. 32, 5387 (1938). For the preparation oftin alkoxides (Formula J) see C.A. 24, 586 (1930). For the preparationof alkyl tin salts (Formula Q) see C.A. 31,4290. For the preparation ofalkyl tin compounds (Formula K and L) see C.A. 35, 2470 (1941): C.A. 33,5357 (1939). For the preparation of mixed alkyl aryl tin (Formulas K andL) see C.A. 31, 4290 (1937): C.A. 38, 331 (1944). For the preparation ofother tin compounds not covered by these citations see “Die Chemie derMetal-Organischen Verbindungen.” by Krause and V. Grosse, published inBerlin, 1937, by Gebroder-Borntrager.

The tin alkoxides (Formulas I and J) and the bimetallic alkoxides(Formulas A through H) contain R substituents which can represent bothstraight chain and branched chain alkyl radicals, e.g. diethoxide,tetramethoxide, tetrabutoxide, tetra-tert-butoxide, tetrahexoxide, etc.

The alkyl derivatives (Formulas K and L) contain one or more alkylradicals attached to a tin atom through a direct C—Sn linkage, e.g.dibutyl tin, dihexyl tin, tetra-butyl tin, tetraethyl tin, tetramethyltin, dioctyl tin, etc. Two of the tetraalkyl radicals can be replacedwith an oxygen atom to form compounds having Formula M, e.g. dimethyltin oxide, diethyl tin oxide, dibutyl tin oxide, diheptyl tin oxide,etc. In one embodiment, the tin catalyst comprises dimethyl tin oxide.

Complexes can be formed by reacting dialkyl tin oxides with alkali metalalkoxides in an alcohol solution to form compounds having Formula N,which compounds are especially useful catalysts, e.g. react dibutyl tinoxide with sodium ethoxide, etc. This formula is intended to representthe reaction products described. Tin compounds containing alkyl andalkoxy radicals are also useful catalysts (see Formula O), e.g. diethyltin diethoxide, dibutyl tin dibutoxide, dihexyl tin dimethoxide, etc.

Salts derived from dialkyl tin oxides reacted with carboxylic acids orhydrochloric acid are also of particular value as catalysts; seeFormulas P and Q. Examples of these catalytic condensing agents includedibutyl tin diacetate, diethyl tin dibutyrate, dibutyl tin dilauroate,dimethyl tin dibenzoate, dibutyl tin dichloride, diethyl tin dichloride,dioctyl tin dichloride, dihexyl tin distearate, etc.

The tin compounds having Formulas K, L and M can be prepared wherein oneor more of the R′ radicals represents an aryl radical of the benzeneseries, e.g. phenyl, tolyl, benzyl, etc. Examples include diphenyl tin,tetraphenyl tin, diphenyl dibutyl tin, ditolyl diethyl tin, diphenyl tinoxide, dibenzyl tin, tetrabenzyl tin, di([B-phenylethyl) tin oxide,dibenzyl tin oxide, etc.

Examples of catalysts useful in the present invention include, but arenot limited to, one of more of the following: butyltintris-2-ethylhexanoate, dibutyltin diacetate, dibutyltin oxide, anddimethyl tin oxide.

In one embodiment, catalysts useful in the present invention include,but are not limited to, one or more of the following: butyltintris-2-ethylhexanoate, dibutyltin diacetate, dibutyltin oxide, anddimethyl tin oxide.

Processes for preparing polyesters using tin-based catalysts are wellknown and described in the aforementioned U.S. Pat. No. 2,720,507.

The polyester portion of the polyester compositions useful in theinvention can be made by processes known from the literature such as,for example, by processes in homogenous solution, by transesterificationprocesses in the melt, and by two phase interfacial processes. Suitablemethods include, but are not limited to, the steps of reacting one ormore dicarboxylic acids with one or more glycols at a temperature of100° C. to 315° C. at a pressure of 0.1 to 760 mm Hg for a timesufficient to form a polyester. See U.S. Pat. No. 3,772,405 for methodsof producing polyesters, the disclosure regarding such methods is herebyincorporated herein by reference.

The polyester in general may be prepared by condensing the dicarboxylicacid or dicarboxylic acid ester with the glycol in the presence of thetin catalyst described herein at elevated temperatures increasedgradually during the course of the condensation up to a temperature ofabout 2250-310° C., in an inert atmosphere, and conducting thecondensation at low pressure during the latter part of the condensation,as described in further detail in U.S. Pat. No. 2,720,507 incorporatedherein by reference.

In another aspect, this invention relates to a process for preparingcopolyesters of the invention. In one embodiment, the process relates topreparing copolyesters comprising terephthalic acid,2,2,4,4-tetramethyl-1,3-cyclobutanediol, and 1,4-cyclohexanedimethanol.This process comprises the steps of:

-   (A) heating a mixture comprising the monomers useful in the    polyesters of the invention in the presence of at least one tin    catalyst and at least one phosphorus compound at a temperature of    150 to 250° C. for a time sufficient to produce an initial    polyester;-   (B) polycondensing the product of Step (A) by heating it at a    temperature of 240 to 320° C. for 1 to 6 hours; and-   (C) removing any unreacted glycols.

Reaction times for the esterification Step (A) are dependent upon theselected temperatures, pressures, and feed mole ratios of glycol todicarboxylic acid.

In one embodiment, step (A) can be carried out until 50% by weight ormore of the 2,2,4,4-tetramethyl-1,3-cyclobutanediol has been reacted.Step (A) may be carried out under pressure, ranging from 0 psig to 100psig. The term “reaction product” as used in connection with any of thecatalysts useful in the invention refers to any product of apolycondensation or esterification reaction with the catalyst and any ofthe monomers used in making the polyester as well as the product of apolycondensation or esterification reaction between the catalyst and anyother type of additive.

Typically, Step (B) and Step (C) can be conducted at the same time.These steps can be carried out by methods known in the art such as byplacing the reaction mixture under a pressure ranging, from 0.002 psigto below atmospheric pressure, or by blowing hot nitrogen gas over themixture.

In one embodiment, the invention comprises a process for making any ofthe polyesters useful in the invention, comprising the following steps:

-   -   (I) heating a mixture at least one temperature chosen from        150° C. to 200° C., under at least one pressure chosen from the        range of 0 psig to 70 psig wherein said mixture comprises:        -   (a) a dicarboxylic acid component comprising:            -   (i) 70 to 100 mole % of terephthalic acid residues;            -   (ii) 0 to 30 mole % of aromatic dicarboxylic acid                residues having up to 20 carbon atoms; and            -   (iii) 0 to 10 mole % of aliphatic dicarboxylic acid                residues having up to 16 carbon atoms; and        -   (b) a glycol component comprising:            -   (i) 1 to 99 mole % of                2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and            -   (ii) 1 to 99 mole % of cyclohexanedimethanol residues;        -   wherein the molar ratio of glycol component/dicarboxylic            acid component added in Step (I) is 1.0-1.5/1.0;        -   wherein the mixture in Step (I) is heated in the presence            of:        -   (i) at least one catalyst comprising at least one tin            compound, and, optionally, at least one catalyst chosen from            titanium, gallium, zinc, antimony, cobalt, manganese,            magnesium, germanium, lithium, aluminum compounds and an            aluminum compound with lithium hydroxide or sodium            hydroxide;    -   (II) heating the product of Step (I) at a temperature of 230° C.        to 320° C. for 1 to 6 hours, under at least one pressure chosen        from the range of the final pressure of Step (I) to 0.02 torr        absolute, to form a final polyester;        wherein the total mole % of the dicarboxylic acid component of        the final polyester is 100 mole %; and wherein the total mole %        of the glycol component of the final polyester is 100 mole %.

In one embodiment, the invention comprises a process for making any ofthe polyesters useful in the invention comprising the following steps:

-   -   (I) heating a mixture at least one temperature chosen from        150° C. to 200° C., under at least one pressure chosen from the        range of 0 psig to 75 psig wherein said mixture comprises:        -   (a) a dicarboxylic acid component comprising:            -   (i) 70 to 100 mole % of terephthalic acid residues;            -   (ii) 0 to 30 mole % of aromatic dicarboxylic acid                residues having up to 20 carbon atoms; and            -   (iii) 0 to 10 mole % of aliphatic dicarboxylic acid                residues having up to 16 carbon atoms; and        -   (b) a glycol component comprising:            -   (i) 1 to 99 mole % of                2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and            -   (ii) 1 to 99 mole % of cyclohexanedimethanol residues;        -   wherein the molar ratio of glycol component/dicarboxylic            acid component added in Step (I) is 1.0-1.5/1.0;        -   wherein the mixture in Step (I) is heated in the presence of            at least one catalyst comprising at least one tin compound,            and, optionally, at least one catalyst chosen from titanium,            gallium, zinc, antimony, cobalt, manganese, magnesium,            germanium, lithium, aluminum compounds and an aluminum            compound with lithium hydroxide or sodium hydroxide; and    -   (II) heating the product of Step (I) at a temperature of 230° C.        to 320° C. for 1 to 6 hours, under at least one pressure chosen        from the range of the final pressure of Step (I) to 0.02 torr        absolute, to form a final polyester;        wherein the total mole % of the dicarboxylic acid component of        the final polyester is 100 mole %;        wherein the total mole % of the glycol component of the final        polyester is 100 mole %;        wherein at least one phosphorus compound, for example, at least        one phosphate ester, is added to Step (I), Step (II) and/or both        Steps (I) and (II); and        wherein the addition of the phosphorus compound(s), for example,        at least one phosphate ester, results in a weight ratio of total        tin atoms to total phosphorus atoms in the final polyester        useful in the invention of 2-10:1.

For example, in the previous two paragraphs, at least one phosphoruscompound can be added in Step (I), (II) and/or in both Steps (I) and(II) of the process. In one embodiment, the phosphorus compound(s) areadded in Step (I). The phosphorus compounds can comprise at least onephosphate ester, for example.

In any of the processes of the invention useful in making the polyestersuseful in the invention, at least one thermal stabilizer, reactionproducts thereof, and mixtures thereof can be added either duringesterification, polycondensation, or both and/or it can be addedpost-polymerization. In one embodiment, the thermal stabilizer useful inany of the processes of the invention can be added duringesterification. In one embodiment, if the thermal stabilizer added afterboth esterification and polycondensation, it is added in the amount of 1to 2 weight % based on the total weight of the final polyester. In oneembodiment, the thermal stabilizer can comprise at least one phosphoruscompound useful in the invention. In one embodiment, the thermalstabilizer can comprise at least one phosphate ester. In one embodiment,the thermal stabilizer can comprise at least one phosphorus compoundwhich is added during the esterification step. In one embodiment, thethermal stabilizer can comprise at least one phosphate ester, forexample, which is added during the esterification step.

In one embodiment, it is believed that when at least one thermalstabilizer comprising at least one phosphorus compound described hereinare used during the processes of making the polyesters according to thepresent invention, the polyesters can be more easily produced without atleast one of the following occurring: bubbling, splay formation, colorformation, foaming, off-gassing, and erratic melt levels, i.e.,pulsating of the polyester or the polyester's production and processingsystems. In another embodiment, it is believed that at least one processof the invention provides a means to more easily produce the polyestersuseful in the invention in large quantities (for example, pilot runscale and/or commercial production) without at least one of theaforesaid difficulties occurring.

The term “large quantities” as used herein includes quantities ofpolyester(s) useful in the invention which are produced in quantitieslarger than 100 pounds. In one embodiment, the term “large quantities,as used herein, includes quantities of polyester(s) useful in theinvention which are produced in quantities larger than 1000 pounds.

In one aspect, the processes of making the polyesters useful in theinvention can comprise a batch or continuous process.

In one aspect, the processes of making the polyesters useful in theinvention comprise a continuous process.

It is believed that any of the processes of making the polyesters usefulin the invention may be used to make any of the polyesters useful in theinvention.

Reaction times for the esterification Step (I) are dependent upon theselected temperatures, pressures, and feed mole ratios of glycol todicarboxylic acid.

In one embodiment, the pressure used in Step (II) of any of theprocesses of the invention consists of at least one pressure chosen from20 torr absolute to 0.02 torr absolute; in one embodiment, the pressureused in Step (II) of any of the processes of the invention consists ofat least one pressure chosen from 10 torr absolute to 0.02 torrabsolute; in one embodiment, the pressure used in Step (II) of any ofthe processes of the invention consists of at least one pressure chosenfrom 5 torr absolute to 0.02 torr absolute; in one embodiment, thepressure used in Step (II) of any of the processes of the inventionconsists of at least one pressure chosen from 3 torr absolute to 0.02torr absolute; in one embodiment, the pressure used in Step (II) of anyof the processes of the invention consists of at least one pressurechosen from 20 torr absolute to 0.1 torr absolute; in one embodiment,the pressure used in Step (II) of any of the processes of the inventionconsists of at least one pressure chosen from 10 torr absolute to 0.1torr absolute; in one embodiment, the pressure used in Step (II) of anyof the processes of the invention consists of at least one pressurechosen from 5 torr absolute to 0.1 torr absolute; in one embodiment, thepressure used in Step (II) of any of the processes of the inventionconsists of at least one pressure chosen from 3 torr absolute to 0.1torr absolute.

In one embodiment, the molar ratio of glycol component/dicarboxylic acidcomponent added in Step (I) of any of the processes of the invention is1.0-1.5/1.0; in one embodiment, the molar ratio of glycolcomponent/dicarboxylic acid component added in Step (I) of any of theprocesses of the invention is 1.01-1.5/1.0; in one embodiment, the molarratio of glycol component/dicarboxylic acid component added in Step (I)of any of the processes of the invention is 1.01-1.3/1.0; in oneembodiment, the molar ratio of glycol component/dicarboxylic acidcomponent added in Step (I) of any of the processes of the invention is1.01-1.2/1.0; in one embodiment, the molar ratio of glycolcomponent/dicarboxylic acid component added in Step (I) of any of theprocesses of the invention is 1.01-1.15/1.0; in one embodiment, themolar ratio of glycol component/dicarboxylic acid component added inStep (I) of any of the processes of the invention is 1.01-1.10/1.0; inone embodiment, the molar ratio of glycol component/dicarboxylic acidcomponent added in Step (I) of any of the processes of the invention is1.03-1.5/1.0; in one embodiment, the molar ratio of glycolcomponent/dicarboxylic acid component added in Step (I) of any of theprocesses of the invention is 1.03-1.3/1.0; in one embodiment, the molarratio of glycol component/dicarboxylic acid component added in Step (I)of any of the processes of the invention is 1.03-1.2/1.0; in oneembodiment, the molar ratio of glycol component/dicarboxylic acidcomponent added in Step (I) of any of the processes of the invention is1.03-1.15/1.0; in one embodiment, the molar ratio of glycol componentdicarboxylic acid component added in Step (I) of any of the processes ofthe invention is 1.03-1.10/1.0; in one embodiment, the molar ratio ofglycol component/dicarboxylic acid component added in Step (I) of any ofthe processes of the invention is 1.05-1.5/1.0; in one embodiment, themolar ratio of glycol component/dicarboxylic acid component added inStep (I) of any of the processes of the invention is 1.05-1.3/1.0; inone embodiment, the molar ratio of glycol component/dicarboxylic acidcomponent added in Step (I) of any of the processes of the invention is1.05-1.2/1.0; in one embodiment, the molar ratio of glycolcomponent/dicarboxylic acid component added in Step (I) of any of theprocesses of the invention is 1.05-1.15/1.0; and in one embodiment, themolar ratio of glycol component/dicarboxylic acid component added inStep (I) of any of the processes of the invention is 1.01-1.10/1.0.

In any of the process embodiments for making the polyesters useful inthe invention, the heating time of Step (II) can be from 1 to 5 hours or1 to 4 hours or 1 to 3 hours or 1.5 to 3 hours or 1 to 2 hours. In oneembodiment, the heating time of Step (II) can be from 1.5 to 3 hours.

In one embodiment, the addition of the phosphorus compound(s) in theprocess(es) of the invention can result in a weight ratio of total tinatoms to total phosphorus atoms in the final polyester useful in theinvention of 2-10:1. In one embodiment, the addition of the phosphoruscompound(s) in the process(es) can result in a weight ratio of total tinatoms to total phosphorus atoms in the final polyester of 5-9:1. In oneembodiment, the addition of the phosphorus compound(s) in theprocess(es) can result in a weight ratio of total tin atoms to totalphosphorus atoms in the final polyester of 6-8:1. In one embodiment, theaddition of the phosphorus compound(s) in the process(es) can result ina weight ratio of total tin atoms to total phosphorus atoms in the finalpolyester of 7:1. For example, the weight of tin atoms and phosphorusatoms present in the final polyester can be measured in ppm and canresult in a weight ratio of total tin atoms to total phosphorus atoms inthe final polyester of any of the aforesaid weight ratios.

In one embodiment, the amount of tin atoms in the final polyester usefulin the invention can be from 15 to 400 ppm tin atoms based on the weightof the final polyester.

In one embodiment, the amount of tin atoms in the final polyester usefulin the invention can be from 25 to 400 ppm tin atoms based on the weightof the final polyester.

In one embodiment, the amount of tin atoms in the final polyester usefulin the invention can be from 40 to 200 ppm tin atoms based on the weightof the final polyester.

In one embodiment, the amount of tin atoms in the final polyester usefulin the invention can be from 50 to 125 ppm tin atoms based on the weightof the final polyester.

In one embodiment, the amount of phosphorus atoms in the final polyesteruseful in the invention can be from 1 to 100 ppm phosphorus atoms basedon the weight of the final polyester.

In one embodiment, the amount of phosphorus atoms in the final polyesteruseful in the invention can be from 4 to 60 ppm phosphorus atoms basedon the weight of the final polyester.

In one embodiment, the amount of phosphorus atoms in the final polyesteruseful in the invention can be from 6 to 20 ppm phosphorus atoms basedon the weight of the final polyester.

In one embodiment, the amount of phosphorus atoms in the final polyesteruseful in the invention can be from 1 to 100 ppm phosphorus atoms basedon the weight of the final polyester and the amount of tin atoms in thefinal polyester can be from 15 to 400 ppm tin atoms based on the weightof the final polyester.

In one embodiment, the amount of phosphorus atoms in the final polyesteruseful in the invention can be from 1 to 100 ppm phosphorus atoms basedon the weight of the final polyester and the amount of tin atoms in thefinal polyester can be from 25 to 400 ppm tin atoms based on the weightof the final polyester.

In one embodiment, the amount of phosphorus atoms in the final polyesteruseful in the invention can be from 4 to 60 ppm phosphorus atoms basedon the weight of the final polyester and the amount of tin atoms in thefinal polyester can be from 40 to 200 ppm tin atoms based on the weightof the final polyester.

In one embodiment, the amount of phosphorus atoms in the final polyesteruseful in the invention can be from 6 to 20 ppm phosphorus atoms basedon the weight of the final polyester and the amount of tin atoms in thefinal polyester can be from 50 to 125 ppm tin atoms based on the weightof the final polyester.

The invention further relates to the polyester compositions made by theprocess(es) described above.

The invention further relates to a polymer blend. The blend comprises:

-   -   (a) 5 to 95 wt % of at least one of the polyesters described        above; and    -   (b) 5 to 95 wt % of at least one polymeric components.

Suitable examples of the polymeric components include, but are notlimited to, nylon, polyesters different from those described herein,polyamides such as ZYTEL® from DuPont; polystyrene, polystyrenecopolymers, stryrene acrylonitrile copolymers, acrylonitrile butadienestyrene copolymers, poly(methylmethacrylate), acrylic copolymers,poly(ether-imides) such as ULTEM® (a poly(ether-imide) from GeneralElectric); polyphenylene oxides such as poly(2,6-dimethylphenyleneoxide) or poly(phenylene oxide)/polystyrene blends such as NORYL 1000®(a blend of poly(2,6-dimethylphenylene oxide) and polystyrene resinsfrom General Electric); polyphenylene sulfides; polyphenylenesulfide/sulfones; poly(ester-carbonates); polycarbonates such as LEXAN®(a polycarbonate from General Electric); polysulfones; polysulfoneethers; and poly(ether-ketones) of aromatic dihydroxy compounds; ormixtures of any of the foregoing polymers. The blends can be prepared byconventional processing techniques known in the art, such as meltblending or solution blending. In one embodiment, the polycarbonate isnot present in the polyester composition. If polycarbonate is used in ablend in the polyester compositions useful in the invention, the blendscan be visually clear. However, the polyester compositions useful in theinvention also contemplate the exclusion of polycarbonate as well as theinclusion of polycarbonate.

Polycarbonates useful in the invention may be prepared according toknown procedures, for example, by reacting the dihydroxyaromaticcompound with a carbonate precursor such as phosgene, a haloformate or acarbonate ester, a molecular weight regulator, an acid acceptor and acatalyst. Methods for preparing polycarbonates are known in the art andare described, for example, in U.S. Pat. No. 4,452,933, where thedisclosure regarding the preparation of polycarbonates is herebyincorporated by reference herein.

Examples of suitable carbonate precursors include, but are not limitedto, carbonyl bromide, carbonyl chloride, or mixtures thereof; diphenylcarbonate; a di(halophenyl)carbonate, e.g., di(trichlorophenyl)carbonate, di(tribromophenyl) carbonate, and the like;di(alkylphenyl)carbonate, e.g., di(tolyl)carbonate;di(naphthyl)carbonate; di(chloronaphthyl)carbonate, or mixtures thereof;and bis-haloformates of dihydric phenols.

Examples of suitable molecular weight regulators include, but are notlimited to, phenol, cyclohexanol, methanol, alkylated phenols, such asoctylphenol, para-tertiary-butyl-phenol, and the like. In oneembodiment, the molecular weight regulator is phenol or an alkylatedphenol.

The acid acceptor may be either an organic or an inorganic acidacceptor. A suitable organic acid acceptor can be a tertiary amine andincludes, but is not limited to, such materials as pyridine,triethylamine, dimethylaniline, tributylamine, and the like. Theinorganic acid acceptor can be either a hydroxide, a carbonate, abicarbonate, or a phosphate of an alkali or alkaline earth metal.

The catalysts that can be used include, but are not limited to, thosethat typically aid the polymerization of the monomer with phosgene.Suitable catalysts include, but are not limited to, tertiary amines suchas triethylamine, tripropylamine, N,N-dimethylaniline, quaternaryammonium compounds such as, for example, tetraethylammonium bromide,cetyl triethyl ammonium bromide, tetra-n-heptylammonium iodide,tetra-n-propyl ammonium bromide, tetramethyl ammonium chloride,tetra-methyl ammonium hydroxide, tetra-n-butyl ammonium iodide,benzyltrimethyl ammonium chloride and quaternary phosphonium compoundssuch as, for example, n-butyltriphenyl phosphonium bromide andmethyltriphenyl phosphonium bromide.

The polycarbonates useful in the polyester compositions of the inventionalso may be copolyestercarbonates such as those described in U.S. Pat.Nos. 3,169,121; 3,207,814; 4,194,038; 4,156,069; 4,430,484, 4,465,820,and 4,981,898, where the disclosure regarding copolyestercarbonates fromeach of the U.S. patents is incorporated by reference herein.

Copolyestercarbonates useful in this invention can be availablecommercially and/or can prepared by known methods in the art. Forexample, they can be typically obtained by the reaction of at least onedihydroxyaromatic compound with a mixture of phosgene and at least onedicarboxylic acid chloride, especially isophthaloyl chloride,terephthaloyl chloride, or both.

In addition, the polyester compositions and the polymer blendcompositions containing the polyesters of this invention may alsocontain from 0.01 to 25% by weight or 0.01 to 20% by weight or 0.01 to15% by weight or 0.01 to 10% by weight or 0.01 to 5% by weight of thetotal weight of the polyester composition of common additives such ascolorants, dyes, mold release agents, flame retardants, plasticizers,nucleating agents, stabilizers, including but not limited to, UVstabilizers, thermal stabilizers and/or reaction products thereof,fillers, and impact modifiers. Examples of typical commerciallyavailable impact modifiers well known in the art and useful in thisinvention include, but are not limited to, ethylene/propyleneterpolymers; functionalized polyolefins, such as those containing methylacrylate and/or glycidyl methacrylate; styrene-based block copolymericimpact modifiers; and various acrylic core/shell type impact modifiers.For example, UV additives can be incorporated into articles ofmanufacture through addition to the bulk, through application of a hardcoat, or through coextrusion of a cap layer. Residues of such additivesare also contemplated as part of the polyester composition.

The polyesters of the invention can comprise at least one chainextender.

Suitable chain extenders include, but are not limited to,multifunctional (including, but not limited to, bifunctional)isocyanates, multifunctional epoxides, including for example, epoxylatednovolacs, and phenoxy resins. In certain embodiments, chain extendersmay be added at the end of the polymerization process or after thepolymerization process. If added after the polymerization process, chainextenders can be incorporated by compounding or by addition duringconversion processes such as injection molding or extrusion. The amountof chain extender used can vary depending on the specific monomercomposition used and the physical properties desired but is generallyabout 0.1 percent by weight to about 10 percent by weight, preferablyabout 0.1 to about 5 percent by weight based on the total weight of thepolyester.

Reinforcing materials may be useful in the compositions of thisinvention. The reinforcing materials may include, but are not limitedto, carbon filaments, silicates, mica, clay, talc, titanium dioxide,Wollastonite, glass flakes, glass beads and fibers, and polymeric fibersand combinations thereof. In one embodiment, the reinforcing materialsare glass, such as fibrous glass filaments, mixtures of glass and talc,glass and mica, and glass and polymeric fibers.

In another embodiment, the invention further relates to articles ofmanufacture comprising any of the polyesters and blends described above.

In another embodiment, the invention further relates to articles ofmanufacture comprising any of the polyesters and blends describedherein. extruded, calendered, and/or molded articles including but notlimited to, injection molded articles, extruded articles, cast extrusionarticles, profile extrusion articles, melt spun articles, thermoformedarticles, extrusion molded articles, injection blow molded articles,injection stretch blow molded articles, extrusion blow molded articles,and extrusion stretch blow molded articles. These articles can include,but are not limited, to films, bottles (including, but not limited to,baby bottles), containers, sheet and/or fibers.

The present polyesters and/or polyester blend compositions can be usefulin forming fibers, films, molded articles, containers, and sheeting. Themethods of forming the polyesters into fibers, films, molded articles,containers, and sheeting are well known in the art. Examples ofpotential molded articles include without limitation: medical devicessuch as dialysis equipment, medical packaging, healthcare supplies,commercial food service products such as food pans, tumblers and storageboxes, baby bottles, food processors, blender and mixer bowls, utensils,water bottles, crisper trays, washing machine fronts, and vacuum cleanerparts. Other potential molded articles could include, but are notlimited to, ophthalmic lenses and frames. For instance, this materialcan be used to make bottles, including but not limited to, baby bottles,as it is clear, tough, heat resistant, and displays good hydrolyticstability.

In another embodiment, the invention further relates to articles ofmanufacture comprising the film(s) and/or sheet(s) containing polyestercompositions described herein.

The films and/or sheets useful in the present invention can be of anythickness which would be apparent to one of ordinary skill in the art.In one embodiment, the film(s) of the invention have a thickness of nomore than 40 mils. In one embodiment, the film(s) of the invention havea thickness of no more than 35 mils. In one embodiment, the film(s) ofthe invention have a thickness of no more than 30 mils. In oneembodiment, the film(s) of the invention have a thickness of no morethan 25 mils. In one embodiment, the film(s) of the invention have athickness of no more than 20 mils.

In one embodiment, the sheet(s) of the invention have a thickness of noless than 20 mils. In another embodiment, the sheet(s) of the inventionhave a thickness of no less than 25 mils. In another embodiment, thesheet(s) of the invention have a thickness of no less than 30 mils. Inanother embodiment, the sheet(s) of the invention have a thickness of noless than 35 mils. In another embodiment, the sheet(s) of the inventionhave a thickness of no less than 40 mils.

The invention further relates to the film(s) and/or sheet(s) comprisingthe polyester compositions of the invention. The methods of forming thepolyesters into film(s) and/or sheet(s) are well known in the art.Examples of film(s) and/or sheet(s) of the invention including but notlimited to extruded film(s) and/or sheet(s), calendered film(s) and/orsheet(s), compression molded film(s) and/or sheet(s), solution castedfilm(s) and/or sheet(s). Methods of making film and/or sheet include butare not limited to extrusion, calendering, compression molding, andsolution casting.

Examples of potential articles made from film and/or sheet useful in theinvention include, but are not limited, to uniaxially stretched film,biaxially stretched film, shrink film (whether or not uniaxially orbiaxially stretched, liquid crystal display film (including but notlimited to diffuser sheets, compensation films and protective films),thermoformed sheet, graphic arts film, outdoor signs, skylights,coating(s), coated articles, painted articles, laminates, laminatedarticles, and/or multiwall films or sheets.

“Graphic art film,” as used herein, is a film having a thermally-curableink (e.g., heat-curable ink or air-curable ink) or radiation-curable ink(e.g., ultra-violet-curable ink) printed thereon or therein. “Curable”refers to capable of undergoing polymerization and/or crosslinking. Inaddition to the ink, the graphic art film may optionally also includevarnishes, coatings, laminates, and adhesives.

Exemplary thermally or air-cured inks involve pigment(s) dispersed inone or more standard carrier resins. The pigment can be 4B Toner (PR57),2B Toner (PR48), Lake Red C (PR53), lithol red (PR49), iron oxide(PR101), Permanent Red R (PR4), Permanent Red 2G (PO5), pyrazoloneorange (PO13), diaryl yellows (PY12, 13,14), monoazo yellows (PY3,5,98),phthalocyanine green (PG7), phthalocyanine Blue, β form (PB15),ultramarine (PB62), permanent violet (PV23), titanium dioxide (PW6),carbon black (furnace/channel) (PB7), PMTA pink, green, blue, violet(PR81, PG1, PB1, PV3), copper ferrocyanide dye complexes (PR169, PG45,PB62, PV27), or the like. (Parenthetical identifications in theforegoing refer to the generic color index prepared by the Society ofDyers and Colourists.) Such pigments and combinations thereof can beused to obtain various colors including, but not limited to, white,black, blue, violet, red, green, yellow, cyan, magenta, or orange.

Other exemplary inks, including radiation-cured inks are disclosed inU.S. Pat. No. 5,382,292, where the disclosure of such inks areincorporated herein by reference.

Examples of typical carrier resins used in standard inks include thosewhich have nitrocellulose, amide, urethane, epoxide, acrylate, and/orester functionalities. Standard carrier resins include one or more ofnitrocellulose, polyamide, polyurethane, ethyl cellulose, celluloseacetate propionate, (meth)acrylates, poly(vinyl butyral), poly(vinylacetate), poly(vinyl chloride), and the like. Such resins can beblended, with widely used blends including nitrocellulose/polyamide andnitrocellulose/polyurethane.

Ink resin(s) normally can be solvated or dispersed in one or moresolvents. Typical solvents employed include, but are not limited to,water, alcohols (e.g., ethanol, 1-propanol, isopropanol, etc.), acetates(e.g., n-propyl acetate), aliphatic hydrocarbons, aromatic hydrocarbons(e.g., toluene), and ketones. Such solvents typically can beincorporated in amounts sufficient to provide inks having viscosities,as measured on a #2 Zahn cup as known in the art, of at least 15seconds, such as at least 20 seconds, at least 25 seconds, or from 25 to35 seconds. In one embodiment, the polyesters have sufficient Tg valuesto allow thermoformability, and to allow ease of printing onto thegraphic art film.

In one embodiment, the graphic art film has at least one property chosenfrom thermoformability, toughness, clarity, chemical resistance, Tg, andflexibility.

Graphic art films can be used in a variety of applications, such as, forexample, in-mold decorated articles, embossed articles, hard-coatedarticles. The graphic art film can be smooth or textured.

Exemplary graphic art films include, but are not limited to, nameplates;membrane switch overlays (e.g., for an appliance); point of purchasedisplays; flat or in-mold decorative panels on washing machines; flattouch panels on refrigerators (e.g., capacitive touch pad arrays); flatpanel on ovens; decorative interior trim for automobiles (e.g., apolyester laminate); instrument clusters for automobiles; cell phonecovers; heating and ventilation control displays; automotive consolepanels; automotive gear shift panels; control displays or warningsignals for automotive instrument panels; facings, dials or displays onhousehold appliances; facings, dials or displays on washing machines;facings, dials or displays on dishwashers; keypads for electronicdevices; keypads for mobile phones, personal digital assistants (PDAs,or hand-held computers) or remote controls; displays for electronicdevices; displays for hand-held electronic devices such as phones andPDAs; panels and housings for mobile or standard phones; logos onelectronic devices; and logos for hand-held phones.

Multiwall film or sheet refers to sheet extruded as a profile consistingof multiple layers that are connected to each other by means of verticalribs. Examples of multiwall film or sheet include but are not limited tooutdoor shelters (for example, greenhouses and commercial canopies).

Examples of extruded articles comprising the polyester compositionsuseful in this invention include, but are not limited to, thermoformedsheet, film for graphic arts applications, outdoor signs, skylights,multiwall film, plastic film for plastic glass laminates, and liquidcrystal display (LCD) films, including but not limited to, diffusersheets, compensation films, and protective films for LCDs.

Other articles within the scope of the invention comprising thepolyester compositions of the invention include but are not limited tosafety/sport (examples including but not limited to: safety shields,face shields, sports goggles [racquetball, ski, etc. . . . ], policeriot shields); corrugated sheet articles; recreation/outdoor vehiclesand devices (examples including but not limited to: lawn tractors, snowmobiles, motorcycle windshield, camper windows, golf cart windshield,jet ski); residential and commercial lighting (examples including butnot limited to: diffusers, office, home and commercial fixtures; HighIntensity Discharge (HID) Lighting); telecommunications/businessequipment/electronics (examples including but not limited to cell phonehousing, TV housing, computer housing, stereo housing, PDAs, etc);optical media; tanning beds; multiwall sheet, extruded articles; rigidmedical packaging; intravenous components; dialysis filter housing;blood therapy containers; sterilization containers (for example, infantcare sterilization containers); pacifiers, tool handles (examplesincluding but not limited to screw drivers, hammer, etc.); thermoplasticarticles; sound barriers; automotive exterior (headlight covers,taillight covers, side windows, sunroof); rigid consumer/industrialpackaging; tubs; showers; hot tubs; machine guards; vending machinedisplay panels; meters; sports and recreation (examples: swimming poolenclosures, stadium seats, hockey rink, open air structures, skigondola); fish aquarium; ophthalmic products, decorative block windows;and interior automotive (instrument clusters).

The invention further relates to bottles described herein. The methodsof forming the polyesters into bottles are well known in the art.Examples of bottles include but are not limited to bottles such aspharmaceutical bottles, baby bottles; water bottles; juice bottles;large commercial water bottles having a weight from 200 to 800 grams;beverage bottles which include but are not limited to two liter bottles,20 ounce bottles, 16.9 ounce bottles; medical bottles; personal carebottles, carbonated soft drink bottles; hot fill bottles; water bottles;alcoholic beverage bottles such as beer bottles and wine bottles; andbottles comprising at least one handle. These bottles include but arenot limited to injection blow molded bottles, injection stretch blowmolded bottles, extrusion blow molded bottles, and extrusion stretchblow molded bottles. Methods of making bottles include but are notlimited to extrusion blow molding, extrusion stretch blow molding,injection blow molding, and injection stretch blow molding. In eachcase, the invention further relates to the preforms (or parisons) usedto make each of said bottles.

These bottles include, but are not limited to, injection blow moldedbottles, injection stretch blow molded bottles, extrusion blow moldedbottles, and extrusion stretch blow molded bottles. Methods of makingbottles include but are not limited to extrusion blow molding, extrusionstretch blow molding, thermoforming, injection blow molding, andinjection stretch blow molding.

Other examples of containers include, but are not limited to, containersfor cosmetics and personal care applications including bottles, jars,vials and tubes; sterilization containers; buffet steam pans; food pansor trays; frozen food trays; microwaveable food trays; hot fillcontainers, amorphous lids or sheets to seal or cover food trays; foodstorage containers; for example, boxes; tumblers, pitchers, cups, bowls,including but not limited to those used in restaurant smallware;beverage containers; retort food containers; centrifuge bowls; vacuumcleaner canisters, and collection and treatment canisters.

“Restaurant smallware,” as used herein, refers to any container used foreating or serving food. Examples of restaurant smallware includepitchers, cups, mugs optionally including handles (including decorativemugs, single- or double walled mugs, pressurized mugs, vacuum mugs),bowls (e.g., serving bowls, soup bowls, salad bowls), and plates (e.g.,eating and serving plates, such as buffet plates, saucers, dinnerplates).

In one embodiment, the containers used as restaurant smallware arecapable of withstanding refrigerator temperatures ranging from greaterthan 0° C. (e.g., 2° C.) to 5° C. In another embodiment, the restaurantsmallware containers can withstand steam treatments and/or commercialdishwasher conditions. In another embodiment, the restaurant smallwarecontainers are capable of withstanding microwave conditions. In oneembodiment, restaurant smallware containers have at least one propertychosen from toughness, clarity, chemical resistance, Tg, hydrolyticstability, and dishwasher stability.

In one embodiment, the medical devices comprising the polyestercompositions of the invention include but are not limited to medicaldevices comprising an ultraviolet light (UV)-curable, silicone-basedcoating, on at least a portion of a surface of a medical devicecomprising a polyester comprising a cyclobutanediol, which improvesprotein resistance and biocompatibility, may be coated on varioussubstrates, and overcomes several difficulties identified in previouslydisclosed methods.

In one embodiment, the present invention comprises a thermoplasticarticle, typically in the form of sheet material, having a decorativematerial embedded therein which comprise any of the compositionsdescribed herein.

“Food storage container,” as used herein, are capable of storing and/orserving hot and/or cold food and/or beverages at temperaturescustomarily used for storing and serving foods and beverages, e.g.,ranging from deep freezer temperatures to hot temperatures such as thosein a low temperature oven or those used in hot beverage dispensers. Inone embodiment, the food storage container can be sealed to reduce therate of food oxidation. In another embodiment, the food storagecontainer can be used to display and serve the food to dining customers.In one embodiment, the food storage containers are capable of beingstored in a freezer, e.g., at temperatures less than 0° C., such astemperatures ranging from −20 to 0° (e.g., −18° C.). In anotherembodiment, the food storage containers are capable of storing food inthe refrigerator at temperatures ranging from greater than 0° C. (e.g.,2° C.) to 5° C. In another embodiment, the food storage containers canwithstand steam treatments and/or commercial dishwasher conditions. Inanother embodiment, the food storage containers are capable ofwithstanding microwave conditions.

Examples of food storage containers include buffet steam pans, buffetsteam trays, food pans, hot and cold beverage dispensers (e.g.refrigerator beverage dispensers, automated hot or cold beveragedispensers), and food storage boxes.

In one embodiment, food storage containers have at least one additionalproperty chosen from toughness, clarity, chemical resistance, Tg, andhydrolytic stability.

In one embodiment of the invention, there is provided a thermoplasticarticle which is obtained by applying heat and pressure to one or morelaminates or “sandwiches”, wherein at least one of said laminatescomprises, in order, (1) at least one upper sheet material, (2) at leastone decorative material, and (3) at least one lower sheet material.Optionally, an adhesive layer may be used between (1) and (2) and/orbetween (2) and (3). Any of layers (1), (2) and/or (3) of the “sandwich”may comprise any of the compositions of the invention.

“Ophthalmic product” as used herein, refers to prescription eyeglasslenses, nonprescription eyeglass lenses, sunglass lenses, and eyeglassand sunglass frames.

In one embodiment, the ophthalmic product is chosen from tinted eyeglasslenses and hardcoated eyeglass lenses. In one embodiment, the eyeglasslenses, such as the tinted eyeglass lenses or hardcoated eyeglasslenses, comprise at least one polarizing film or polarizing additive.

In one embodiment, when the product is a lens, the ophthalmic producthas a refractive index ranging from 1.54 to 1.56.

In one embodiment, the ophthalmic product can have at least one propertychosen from toughness, clarity, chemical resistance (e.g., forwithstanding lens cleaners, oils, hair products, etc.), Tg, andhydrolytic stability.

“Outdoor sign,” as used herein, refers to a surface formed from thepolyester described herein, or containing symbols (e.g., numbers,letters, words, pictures, etc.), patterns, or designs coated with thepolyester or polyester film described herein. In one embodiment, theoutdoor sign comprises a polyester containing printed symbols, patterns,or designs. In one embodiment, the sign is capable of withstandingtypical weather conditions, such as rain, snow, ice, sleet, highhumidity, heat, wind, sunlight, or combinations thereof, for asufficient period of time, e.g., ranging from one day to several yearsor more.

Exemplary outdoor signs include, but are not limited to, billboards,neon signs, electroluminescent signs, electric signs, fluorescent signs,and light emitting diode (LED) displays. Other exemplary signs include,but are not limited to, painted signs, vinyl decorated signs,thermoformed signs, and hardcoated signs.

In one embodiment, the outdoor sign has at least one property chosenfrom thermoformability, toughness, clarity, chemical resistance, and Tg.

A “vending machine display panel,” as used herein, refers to a front orside panel on a vending machine that allows a customer to view the itemsfor sale, or advertisement regarding such items. In one embodiment, thevending machine display panel can be a visually clear panel of a vendingmachine through which a consumer can view the items on sale. In otherembodiments, the vending machine display panel can have sufficientrigidity to contain the contents within the machine and/or to discouragevandalism and/or theft.

In one embodiment, the vending machine display panel can have dimensionswell known in the art, such as planar display panels in snack, beverage,popcorn, or sticker/ticket vending machines, and capsule display panelsas in, e.g., gumball machines or bulk candy machines.

In one embodiment, the vending machine display panel can optionallycontain advertising media or product identification indicia. Suchinformation can be applied by methods well known in the art, e.g., silkscreening.

In one embodiment, the vending machine display panel can be resistant totemperatures ranging from −100 to 120° C. In another embodiment, thevending machine display panel can be UV resistant by the addition of,e.g., at least one UV additive, as disclosed herein.

In one embodiment, the vending machine display panel has at least oneproperty chosen from thermoformability, toughness, clarity, chemicalresistance, and Tg.

“Point of purchase display,” as used herein, refers to a wholly orpartially enclosed casing having at least one visually clear panel fordisplaying an item. Point of purchase displays are often used in retailstores to for the purpose of catching the eye of the customer. Exemplarypoint of purchase displays include enclosed wall mounts, countertops,enclosed poster stands, display cases (e.g., trophy display cases), signframes, and cases for computer disks such as CDs and DVDs. The point ofpurchase display can include shelves, and additional containers, such asholders for magazines or pamphlets. One of ordinary skill in the art canreadily envision the shape and dimensions for the point of purchasedisplay depending on the item to be displayed. For example, the displaycan be as small as a case for jewelry, or a larger enclosed cabinet fordisplaying multiple trophies.

In one embodiment, the point of purchase display has at least oneproperty chosen from toughness, clarity, chemical resistance, Tg, andhydrolytic stability.

“Intravenous component,” as used herein, refers to components made froma polymeric material used for administering fluids (e.g., medicaments,nutrients) to the bloodstream of a patient. In one embodiment, theintravenous component is a rigid component.

Exemplary intravenous components include y-site connector assemblies,luer components, filters, stopcocks, manifolds, and valves. A y-siteconnector has a “Y” shape including a first arm having a first passage,a second arm having a second passage, and a third arm connected withsaid first and second arms and having a third passage communicating withsaid first and second passages. Luer components can include luer locks,connections, and valves.

In one embodiment, the intravenous component can withstand sterilizationtreatments, such as high pressure steam sterilization, ethylene oxidegas sterilization, radiation sterilization, and dry-heatingsterilization. In one embodiment, the intravenous component has at leastone property chosen from toughness, clarity, chemical resistance, Tg,and hydrolytic stability.

A “dialysis filter housing,” as used herein, refers to a protectivecasing having a plurality of openings for holding a plurality of hollowfibers or tubing, which can be used for introducing and discharging adialyzate to a patient. In one embodiment, a cross-sectional area of oneopening in the protective casing ranges from 0.001 cm² to less than 50cm².

In one embodiment, the dialysis filter housing has at least one propertychosen from toughness, clarity, chemical resistance, Tg, and hydrolyticstability.

“Blood therapy containers,” as used herein, refers to those containersused in administering and withdrawing blood to and from a patient.Exemplary blood therapy containers include oxygenators, cassettes,centrifuge bowls, collection and treatment canisters, pump cartridges,venal port housings, and dialyzer housings. Oxygenators can removecarbon dioxide from the venous blood of the patient, introduce oxygen tothe withdrawn blood to convert it into arterial blood, and introduce theoxygenated blood to the patient. Other containers can be used totemporarily house the withdrawn or stored blood prior to itsadministration to the patient.

In one embodiment, the blood therapy container can withstandsterilization treatments, such as high pressure steam sterilization,ethylene oxide gas sterilization, radiation sterilization, anddry-heating sterilization. In one embodiment, the blood therapycontainer has at least one property chosen from toughness, clarity,chemical resistance, Tg, and hydrolytic stability.

“Appliance parts,” as used herein, refers to a rigid piece used inconjunction with an appliance. In one embodiment, the appliance part ispartly or wholly separable from the appliance. In another embodiment,the appliance part is one that is typically made from a polymer. In oneembodiment, the appliance part is visually clear.

Exemplary appliance parts include those requiring toughness anddurability, such as cups and bowls used with food processors, mixers,blenders, and choppers; parts that can withstand refrigerator andfreezer temperatures (e.g., refrigerator temperatures ranging fromgreater than 0° C. (e.g., 2° C.) to 5° C., or freezer temperatures,e.g., at temperatures less than 0° C., such as temperatures ranging from−20 to 0° C., e.g., −18° C.), such as refrigerator and freezer trays,bins, and shelves; parts having sufficient hydrolytic stability attemperatures up to 90° C., such as washing machine doors, steam cleanercanisters, tea kettles, and coffee pots; and vacuum cleaner canistersand dirt cups.

In one embodiment, these appliance parts have at least one propertychosen from toughness, clarity, chemical resistance, Tg, hydrolyticstability, and dishwasher stability. The appliance part can also bechosen from steam cleaner canisters, which, in one embodiment, can haveat least one property chosen from toughness, clarity, chemicalresistance, Tg, and hydrolytic stability.

In one embodiment, the polyester useful in the appliance part has a Tgof 105 to 140° C. and the appliance part is chosen from vacuum cleanercanisters and dirt cups. In another embodiment, the polyester useful inthe appliance part has a Tg of 120 to 150° C. and the appliance part ischosen from steam cleaner canisters, tea kettles and coffee pots.

“Skylight,” as used herein, refers to a light permeable panel secured toa roof surface such that the panel forms a portion of the ceiling. Inone embodiment, the panel is rigid, e.g., has dimensions sufficient toachieve stability and durability, and such dimensions can readily bedetermined by one skilled in the art. In one embodiment, the skylightpanel has a thickness greater than 3/16 inches, such as a thickness ofat least ½ inches.

In one embodiment, the skylight panel is visually clear. In oneembodiment, the skylight panel can transmit at least 35% visible light,at least 50%, at least 75%, at least 80%, at least 90%, or even at least95% visible light. In another embodiment, the skylight panel comprisesat least one UV additive that allows the skylight panel to block up to80%, 90%, or up to 95% UV light.

In one embodiment, the skylight has at least one property chosen fromthermoformability, toughness, clarity, chemical resistance, and Tg.

“Outdoor shelters,” as used herein, refer to a roofed and/or walledstructure capable of affording at least some protection from theelements, e.g., sunlight, rain, snow, wind, cold, etc., having at leastone rigid panel. In one embodiment, the outdoor shelter has at least aroof and/or one or more walls. In one embodiment, the outdoor shelterhas dimensions sufficient to achieve stability and durability, and suchdimensions can readily be determined by one skilled in the art. In oneembodiment, the outdoor shelter panel has a thickness greater than 3/16inches.

In one embodiment, the outdoor shelter panel is visually clear. In oneembodiment, the outdoor shelter panel can transmit at least 35% visiblelight, at least 50%, at least 75%, at least 80%, at least 90%, or evenat least 95% visible light. In another embodiment, the outdoor shelterpanel comprises at least one UV additive that allows the outdoor shelterto block up to 80%, 90%, or up to 95% UV light.

Exemplary outdoor shelters include security glazings, transportationshelters (e.g., bus shelters), telephone kiosks, and smoking shelters.In one embodiment, where the shelter is a transportation shelter,telephone kiosk, or smoking shelter, the shelter has at least oneproperty chosen from thermoformability, toughness, clarity, chemicalresistance, and Tg. In one embodiment, where the shelter is a securityglazing, the shelter has at least one property chosen from toughness,clarity, chemical resistance, and Tg.

A “canopy,” as used herein, refers to a roofed structure capable ofaffording at least some protection from the elements, e.g., sunlight,rain, snow, wind, cold, etc. In one embodiment, the roofed structurecomprises, either in whole or in part, at least one rigid panel, e.g.,has dimensions sufficient to achieve stability and durability, and suchdimensions can readily be determined by one skilled in the art. In oneembodiment, the canopy panel has a thickness greater than 3/16 inches,such as a thickness of at least ½ inches.

In one embodiment, the canopy panel is visually clear. In oneembodiment, the canopy panel can transmit at least 35% visible light, atleast 50%, at least 75%, at least 80%, at least 90%, or even at least95% visible light. In another embodiment, the canopy panel comprises atleast one UV additive that allows the canopy to block up to 80%, 90%, orup to 95% UV light.

Exemplary canopies include covered walkways, roof lights, sun rooms,airplane canopies, and awnings. In one embodiment, the canopy has atleast one property chosen from toughness, clarity, chemical resistance,Tg, and flexibility.

A “sound barrier,” as used herein, refers to a rigid structure capableof reducing the amount of sound transmission from one point on a side ofthe structure to another point on the other side when compared to soundtransmission between two points of the same distance without the soundbarrier. The effectiveness in reducing sound transmission can beassessed by methods known in the art. In one embodiment, the amount ofsound transmission that is reduced ranges from 25% to 90%.

In another embodiment, the sound barrier can be rated as a soundtransmission class value, as described in, for example, ASTM E90,“Standard Test Method for Laboratory Measurement of Airborne SoundTransmission Loss of Building Partitions and Elements,” and ASTM E413,“Classification of Rating Sound Insulation.” An STC 55 barrier canreduce the sound of a jet engine, ˜130 dBA, to 60 dBA, which is thesound level within a typical office. A sound proof room can have a soundlevel ranging from 0-20 dBA. One of ordinary skill in the art canconstruct and arrange the sound barrier to achieve a desired STC rating.In one embodiment, the sound barrier has an STC rating of at least 20,such as a rating ranging from 20 to 60.

In one embodiment, the sound barrier comprises a plurality of panelsconnected and arranged to achieve the desired barrier outline. The soundbarriers can be used along streets and highways to dampen automotivenoises. Alternatively, the sound barriers can be used in the home oroffice, either as a discrete panel or panels, or inserted within thearchitecture of the walls, floors, ceilings, doors, and/or windows.

In one embodiment, the sound barrier is visually clear. In oneembodiment, the sound barrier can transmit at least 35% visible light,at least 50%, at least 75%, at least 80%, at least 90%, or even at least95% visible light. In another embodiment, the sound barrier comprises atleast one UV additive that allows the sound barrier to block up to 80%,90%, or up to 95% UV light.

In one embodiment, the sound barrier has at least one property chosenfrom toughness, clarity, chemical resistance, and Tg.

A “greenhouse,” as used herein, refers to an enclosed structure used forthe cultivation and/or protection of plants. In one embodiment, thegreenhouse is capable of maintaining a humidity and/or gas (oxygen,carbon dioxide, nitrogen, etc.) content desirable for cultivating plantswhile being capable of affording at least some protection from theelements, e.g., sunlight, rain, snow, wind, cold, etc. In oneembodiment, the roof of the greenhouse comprises, either in whole or inpart, at least one rigid panel, e.g., has dimensions sufficient toachieve stability and durability, and such dimensions can readily bedetermined by one skilled in the art. In one embodiment, the greenhousepanel has a thickness greater than 3/16 inches, such as a thickness ofat least ½ inches.

In one embodiment, the greenhouse panel is visually clear. In anotherembodiment, substantially all of the roof and walls of the greenhouseare visually clear. In one embodiment, the greenhouse panel can transmitat least 35% visible light, at least 50%, at least 75%, at least 80%, atleast 90%, or even at least 95% visible light. In another embodiment,the greenhouse panel comprises at least one UV additive that allows thegreenhouse panel to block up to 80%, 90%, or up to 95% UV light.

In one embodiment, the greenhouse panel has at least one property chosenfrom toughness, clarity, chemical resistance, and Tg.

An “optical medium,” as used herein, refers to an information storagemedium in which information is recorded by irradiation with a laserbeam, e.g., light in the visible wavelength region, such as light havinga wavelength ranging from 600 to 700 nm. By the irradiation of the laserbeam, the irradiated area of the recording layer is locally heated tochange its physical or chemical characteristics, and pits are formed inthe irradiated area of the recording layer. Since the opticalcharacteristics of the formed pits are different from those of the areahaving been not irradiated, the digital information is opticallyrecorded. The recorded information can be read by reproducing proceduregenerally comprising the steps of irradiating the recording layer withthe laser beam having the same wavelength as that employed in therecording procedure, and detecting the light-reflection differencebetween the pits and their periphery.

In one embodiment, the optical medium comprises a transparent dischaving a spiral pregroove, a recording dye layer placed in the pregrooveon which information is recorded by irradiation with a laser beam, and alight-reflecting layer. The optical medium is optionally recordable bythe consumer. In one embodiment, the optical medium is chosen fromcompact discs (CDs) and digital video discs (DVDs). The optical mediumcan be sold with prerecorded information, or as a recordable disc.

In one embodiment, at least one of the following comprises the polyesterof the invention: the substrate, at least one protective layer of theoptical medium, and the recording layer of the optical medium.

In one embodiment, the optical medium has at least one property chosenfrom toughness, clarity, chemical resistance, Tg, and hydrolyticstability.

“Infant-care sterilization container,” as used herein, refers to acontainer configured to hold infant-care products for use in in-homesterilization of the infant-care products. In one embodiment, theinfant-care sterilization container is a baby bottle sterilizationcontainer.

In one embodiment, infant-care sterilization containers have at leastone additional property chosen from toughness, clarity, chemicalresistance, Tg, hydrolytic stability, and dishwasher stability.

“Pacifiers” as used herein, comprise a flexible nipple (e.g., for aninfant to suck and/or bite) surrounded by a rigid mouth shield, wherethe rigid mouth shield is optionally connected to a handle, allowing theinfant or supervising adult a convenient structure for gripping and/orholding the pacifier. The handle may be rigid or flexible.

In one embodiment, the pacifier can be made of multiple components. Forexample, the nipple can pass through an aperture in the center of themouth shield. The handle may or may not be integrally connected to themouth shield. The handle can be rigid or flexible.

In another embodiment, the nipple and mouth shield of the pacifier isformed as an integral unit. Generally, the selection of plastic isgoverned by the need to provide a relatively rigid mount shield andhandle. In this embodiment, the nipple of the pacifier may be more rigidyet still be desirable for an infant to suck or bite.

In one embodiment, pacifiers have at least one property chosen fromtoughness, clarity, chemical resistance, Tg, hydrolytic stability, anddishwasher stability.

A “retort food container,” as used herein, refers to flexible containeror pouch for storing food and/or beverages, in which the food and/orbeverage is hermetically sealed for long-term unrefrigerated storage.The food can be sealed under vacuum or an inert gas. The retort foodcontainer can comprise at least one polyester layer, e.g., a singlelayer or multi-layer container. In one embodiment, a multi-layercontainer includes a light reflecting inner layer, e.g., a metallizedfilm.

In one embodiment, at least one foodstuff chosen from vegetables, fruit,grain, soups, meat, meat products, dairy products, sauces, dressings,and baking supplies is contained in the retort food container.

In one embodiment, the retort food container has at least one propertychosen from toughness, clarity, chemical resistance, Tg, and hydrolyticstability.

A “glass laminate,” as used herein, refers to at least one coating on aglass, where at least one of the coatings comprises the polyester. Thecoating can be a film or a sheet. The glass can be clear, tinted, orreflective. In one embodiment, the laminate is permanently bonded to theglass, e.g., applying the laminate under heat and pressure to form asingle, solid laminated glass product. One or both faces of the glasscan be laminated. In certain embodiments, the glass laminate containsmore than one coating comprising the polyester compositions of thepresent invention. In other embodiments, the glass laminate comprisesmultiple glass substrates, and more than one coating comprising thepolyester compositions of the present invention.

Exemplary glass laminates include windows (e.g., windows for high risebuildings, building entrances), safety glass, windshields fortransportation applications (e.g., automotive, buses, jets, armoredvehicles), bullet proof or resistant glass, security glass (e.g., forbanks), hurricane proof or resistant glass, airplane canopies, mirrors,solar glass panels, flat panel displays, and blast resistant windows.The glass laminate can be visually clear, be frosted, etched, orpatterned.

In one embodiment the glass laminate can be resistant to temperaturesranging from −100 to 120° C. In another embodiment, the glass laminatecan be UV resistant by the addition of, e.g., at least one UV additive,as disclosed herein.

Methods for laminating the films and/or sheets of the present inventionto the glass are well known to one of ordinary skill in the art.Lamination without the use of an adhesive layer may be performed byvacuum lamination. To obtain an effective bond between the glass layerand the laminate, in one embodiment, the glass has a low surfaceroughness.

Alternatively, a double-sided adhesive tape, an adhesive layer, or agelatin layer, obtained by applying, for example, a hotmelt, a pressure-or thermo-sensitive adhesive, or a UV or electron-beam curable adhesive,can be used to bond the laminate of the present invention to the glass.The adhesive layer may be applied to the glass sheet, to the laminate,or to both, and may be protected by a stripping layer, which can beremoved just before lamination.

In one embodiment, the glass laminate has at least one property chosenfrom toughness, clarity, chemical resistance, hydrolytic stability, andTg.

As used herein, the abbreviation “wt” means “weight”.

The following examples further illustrate how the compositions of matterof the invention can be made and evaluated, and are intended to bepurely exemplary of the invention and are not intended to limit thescope thereof. Unless indicated otherwise, parts are parts by weight,temperature is in degrees C. or is at room temperature, and pressure isat or near atmospheric.

EXAMPLES

The following examples illustrate in general how a polyester is preparedand the effect of using 2,2,4,4-tetramethyl-1,3-cyclobutanediol (andvarious cis/trans mixtures) on various polyester properties such astoughness, glass transition temperature, inherent viscosity, etc.,compared to polyesters comprising 1,4-cyclohexanedimethanol and/orethylene glycol residues, but lacking2,2,4,4-tetramethyl-1,3-cyclobutanediol. Additionally, based on thefollowing examples, the skilled artisan will understand how the thermalstabilizers of the invention can be used in the preparation ofpolyesters containing them.

Measurement Methods

The inherent viscosity of the polyesters was determined in 60/40 (wt/wt)phenol/tetrachloroethane at a concentration of 0.25 g/50 ml at 25° C.,and is reported in dL/g.

Unless stated otherwise, the glass transition temperature (Tg) wasdetermined using a TA DSC 2920 instrument from Thermal AnalystInstruments at a scan rate of 20° C./min according to ASTM D3418.

The glycol content and the cis/trans ratio of the compositions weredetermined by proton nuclear magnetic resonance (NMR) spectroscopy. AllNMR spectra were recorded on a JEOL Eclipse Plus 600 MHz nuclearmagnetic resonance spectrometer using either chloroform-trifluoroaceticacid (70-30 volume/volume) for polymers or, for oligomeric samples,60/40 (wt/wt) phenol/tetrachlorethane with deuterated chloroform addedfor lock. Peak assignments for 2,2,4,4-tetramethyl-1,3-cyclobutanediolresonances were made by comparison to model mono- and dibenzoate estersof 2,2,4,4-tetramethyl-1,3-cyclobutanediol. These model compoundsclosely approximate the resonance positions found in the polymers andoligomers.

The crystallization half-time, t_(1/2), was determined by measuring thelight transmission of a sample via a laser and photo detector as afunction of time on a temperature controlled hot stage. This measurementwas done by exposing the polymers to a temperature, T_(max), and thencooling it to the desired temperature. The sample was then held at thedesired temperature by a hot stage while transmission measurements weremade as a function of time. Initially, the sample was visually clearwith high light transmission and became opaque as the samplecrystallized. The crystallization half-time was recorded as the time atwhich the light transmission was halfway between the initialtransmission and the final transmission. T_(max) is defined as thetemperature required to melt the crystalline domains of the sample (ifcrystalline domains are present). The T_(max) reported in the examplesbelow represents the temperature at which each sample was heated tocondition the sample prior to crystallization half time measurement. TheT_(max) temperature is dependant on composition and is typicallydifferent for each polyester. For example, PCT may need to be heated tosome temperature greater than 290° C. to melt the crystalline domains.

Density was determined using a gradient density column at 23° C.

The melt viscosity reported herein was measured by using a RheometricsDynamic Analyzer (RDA II). The melt viscosity was measured as a functionof shear rate, at frequencies ranging from 1 to 400 rad/sec, at thetemperatures reported. The zero shear melt viscosity (η_(o)) is the meltviscosity at zero shear rate estimated by extrapolating the data byknown models in the art. This step is automatically performed by theRheometrics Dynamic Analyzer (RDA II) software.

The polymers were dried at a temperature ranging from 80 to 10° C. in avacuum oven for 24 hours and injection molded on a Boy 22S moldingmachine to give ⅛×½×5-inch and ¼×½×5-inch flexure bars. These bars werecut to a length of 2.5 inch and notched down the ½ inch width with a10-mil notch in accordance with ASTM D256. The average Izod impactstrength at 23° C. was determined from measurements on 5 specimens.

In addition, 5 specimens were tested at various temperatures using 5° C.increments in order to determine the brittle-to-ductile transitiontemperature. The brittle-to-ductile transition temperature is defined asthe temperature at which 50% of the specimens fail in a brittle manneras denoted by ASTM D256.

Color values reported herein are CIELAB L*, a*, and b* values measuredfollowing ASTM D 6290-98 and ASTM E308-99, using measurements from aHunter Lab Ultrascan XE Spectrophotometer (Hunter Associates LaboratoryInc., Reston, Va.) with the following parameters: (1) D65 illuminant,(2) 10 degree observer, (3) reflectance mode with specular angleincluded, (4) large area view, (5) 1″ port size. The measurements wereperformed on polymer granules ground to pass a 6 mm sieve.

The percent foam in the polyesters of the invention was measured asfollows. A 20 mL Headspace Vial supplied by MicroLiter AnalyticalSupplies, Suwanee, Ga. was placed on laboratory scale, 5 grams of driedpolymer was added and the weight was recorded. Water was then carefullyadded until the vial was full and this weight was then recorded. Thedifference in weight (wt1) was recorded and used to estimate the vialvolume with polymer containing no foam. This value was used for allsubsequent runs. For each test, 5 grams of dried polymer sample wasadded to a clean Headspace Vial. A septum cap was attached to the top ofthe vial and the vial purged with dry nitrogen gas for approximately oneminute. The purge line was removed and a dry nitrogen line equipped witha bubbler was inserted into the septum cap to ensure inert gas atatmospheric (ambient) pressure was maintained in the vial during theheating time. The vial was then placed into a pre-heated 300° C. heatingblock (drilled out for a loose but close fit for vial) and held in theblock for 15 minutes. The vial was then removed and air-cooled on alaboratory bench. After the vial was cooled, the vial top was removedand the vial was placed on a laboratory scale and weighed. Once theweight was recorded, water was carefully added to completely fill thevial. In this context, to completely fill the vial means to add water tothe top of vial as judged to be the same height as when determining wt1)and the weight recorded. The difference in these weights (wt2) wascalculated. By subtracting wt2 from wt1, the amount of “displaced water”by the foaming of the polymer is determined (wt3=wt1−wt2). It wasassumed that for this test the density of water is one, which allowsthese weights to be converted into volumes, V1=wt1, V2=wt2, and V3=wt3.The “% foam in the polyester” is calculated by the following formula: “%foam in the polymer”=V3/[(5 g polymer/Density of dry polyester ing/mL)+V3]. In this formula, the density of the dry polyesters of theinvention comprising about 45 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol was 1.17 g/mL. This 1.17 g/mLvalue did not change significantly for the polyesters tested with acomposition in the range from 40% to 50% mol TMCD. The density value fordry polyesters of about 20 mole % TCMD was 1.18 g/mL. The % Foam is avolume % of void volume in the after-test polymer. A visual grade of thefinal polymer sample after heating and cooling can also be determined.

The amount of tin (Sn) in the examples below is reported in part permillion (ppm) of metal and was measured by x-ray fluorescence (xrf)using a PANanalytical Axios Advanced wavelength dispersive x-rayfluorescence spectrometer. The amount of phosphorous is similarlyreported as ppm of elemental phosphorus and was also measured by xrfusing the same instrument.

10-mil films of selected polyester samples were compression molded usinga Carver press at 240° C. Inherent viscosity was measured on these filmsas described above.

Unless otherwise specified, the cis/trans ratio of the 1,4cyclohexanedimethanol used in the following examples was approximately30/70, and could range from 35/65 to 25/75. Unless otherwise specified,the cis/trans ratio of the 2,2,4,4-tetramethyl-1,3-cyclobutanediol usedin the following examples was approximately 50/50.

The following abbreviations apply throughout the working examples andfigures:

TPA Terephthalic acid DMT Dimethyl terephthalate TMCD2,2,4,4-tetramethyl-1,3-cyclobutanediol CHDM 1,4-cyclohexanedimethanolIV Inherent viscosity TPP Triphenyl phosphate DBTO Dibutyl tin oxideDMTO Dimethyl tin oxide η_(o) Zero shear melt viscosity T_(g) Glasstransition temperature T_(bd) Brittle-to-ductile transition temperatureT_(max) Conditioning temperature for crystallization half timemeasurements

Example 1

This example illustrates that 2,2,4,4-tetramethyl-1,3-cyclobutanediol ismore effective at reducing the crystallization rate of PCT than ethyleneglycol or isophthalic acid. In addition, this example illustrates thebenefits of 2,2,4,4-tetramethyl-1,3-cyclobutanediol on the glasstransition temperature and density.

A variety of copolyesters were prepared as described below. Thesecopolyesters were all made with 200 ppm dibutyl tin oxide as thecatalyst in order to minimize the effect of catalyst type andconcentration on nucleation during crystallization studies. Thecis/trans ratio of the 1,4-cyclohexanedimethanol was 31/69 while thecis/trans ratio of the 2,2,4,4-tetramethyl-1,3-cyclobutanediol isreported in Table 1.

For purposes of this example, the samples had sufficiently similarinherent viscosities thereby effectively eliminating this as a variablein the crystallization rate measurements.

Crystallization half-time measurements from the melt were made attemperatures from 140 to 200° C. at 10° C. increments and are reportedin Table 1. The fastest crystallization half-time for each sample wastaken as the minimum value of crystallization half-time as a function oftemperature, typically occurring around 170 to 180° C. The fastestcrystallization half-times for the samples are plotted in FIG. 1 as afunction of mole % comonomer modification to PCT.

The data shows that 2,2,4,4-tetramethyl-1,3-cyclobutanediol is moreeffective than ethylene glycol and isophthalic acid at decreasing thecrystallization rate (i.e., increasing the crystallization half-time).In addition, 2,2,4,4-tetramethyl-1,3-cyclobutanediol increases Tg andlowers density.

TABLE 1 Crystallization Half-times (min) at at at at at at at ComonomerIV Density T_(g) T_(max) 140° C. 150° C. 160° C. 170° C. 180° C. 190° C.200° C. Example (mol %)¹ (dl/g) (g/ml) (° C.) (° C.) (min) (min) (min)(min) (min) (min) (min) 1A 20.2% A² 0.630 1.198 87.5 290 2.7 2.1 1.3 1.20.9 1.1 1.5 1B 19.8% B 0.713 1.219 87.7 290 2.3 2.5 1.7 1.4 1.3 1.4 1.71C 20.0% C 0.731 1.188 100.5 290 >180 >60 35.0 23.3 21.7 23.3 25.2 1D40.2% A² 0.674 1.198 81.2 260 18.7 20.0 21.3 25.0 34.0 59.9 96.1 1E34.5% B 0.644 1.234 82.1 260 8.5 8.2 7.3 7.3 8.3 10.0 11.4 1F 40.1% C0.653 1.172 122.0 260 >10 >5 days >5 days 19204 >5 days >5 days >5 daysdays 1G 14.3% D 0.646³ 1.188 103.0 290 55.0 28.8 11.6 6.8 4.8 5.0 5.5 1H15.0% E 0.728⁴ 1.189 99.0 290 25.4 17.1 8.1 5.9 4.3 2.7 5.1 ¹The balanceof the diol component of the polyesters in Table 1 is1,4-cyclohexanedimethanol; and the balance of the dicarboxylic acidcomponent of the polyesters in Table 1 is dimethy terephthalate; if thedicarboxylic acid is not described, it is 100 mole % dimethylterephthalate. ²100 mole % 1,4-cyclohexanedimethanol. ³A film waspressed from the ground polyester of Example 1G at 240° C. The resultingfilm had an inherent viscosity value of 0.575 dL/g. ⁴A film was pressedfrom the ground polyester of Example 1H at 240° C. The resulting filmhad an inherent viscosity value of 0.0.652 dL/g.where:

A is Isophthalic Acid

B is Ethylene Glycol

C is 2,2,4,4-Tetramethyl-1,3-cyclobutanediol (approx. 50/50 cis/trans)

D is 2,2,4,4-Tetramethyl-1,3-cyclobutanediol (98/2 cis/trans)

E is 2,2,4,4-Tetramethyl-1,3-cyclobutanediol (5/95 cis/trans)

As shown in Table 1 and FIG. 1, 2,2,4,4-tetramethyl-1,3-cyclobutanediolis more effective than other comonomers, such ethylene glycol andisophthalic acid, at increasing the crystallization half-time, i.e., thetime required for a polymer to reach half of its maximum crystallinity.By decreasing the crystallization rate of PCT (increasing thecrystallization half-time), amorphous articles based on2,2,4,4-tetramethyl-1,3-cyclobutanediol-modified PCT as described hereinmay be fabricated by methods known in the art. As shown in Table 1,these materials can exhibit higher glass transition temperatures andlower densities than other modified PCT copolyesters.

Preparation of the polyesters shown on Table 1 is described below.

Example 1A

This example illustrates the preparation of a copolyester with a targetcomposition of 80 mol % dimethyl terephthalate residues, 20 mol %dimethyl isophthalate residues, and 100 mol % 1,4-cyclohexanedimethanolresidues (28/72 cis/trans).

A mixture of 56.63 g of dimethyl terephthalate, 55.2 g of1,4-cyclohexanedimethanol, 14.16 g of dimethyl isophthalate, and 0.0419g of dibutyl tin oxide was placed in a 500-milliliter flask equippedwith an inlet for nitrogen, a metal stirrer, and a short distillationcolumn. The flask was placed in a Wood's metal bath already heated to210° C. The stirring speed was set to 200 RPM throughout the experiment.The contents of the flask were heated at 210° C. for 5 minutes and thenthe temperature was gradually increased to 290° C. over 30 minutes. Thereaction mixture was held at 290° C. for 60 minutes and then vacuum wasgradually applied over the next 5 minutes until the pressure inside theflask reached 100 mm of Hg. The pressure inside the flask was furtherreduced to 0.3 mm of Hg over the next 5 minutes. A pressure of 0.3 mm ofHg was maintained for a total time of 90 minutes to remove excessunreacted diols. A high melt viscosity, visually clear and colorlesspolymer was obtained with a glass transition temperature of 87.5° C. andan inherent viscosity of 0.63 dl/g. NMR analysis showed that the polymerwas composed of 100 mol % 1,4-cyclohexanedimethanol residues and 20.2mol % dimethyl isophthalate residues.

Example 1B

This example illustrates the preparation of a copolyester with a targetcomposition of 100 mol % dimethyl terephthalate residues, 20 mol %ethylene glycol residues, and 80 mol % 1,4-cyclohexanedimethanolresidues (32/68 cis/trans).

A mixture of 77.68 g of dimethyl terephthalate, 50.77 g of1,4-cyclohexanedimethanol, 27.81 g of ethylene glycol, and 0.0433 g ofdibutyl tin oxide was placed in a 500-milliliter flask equipped with aninlet for nitrogen, a metal stirrer, and a short distillation column.The flask was placed in a Wood's metal bath already heated to 200° C.The stirring speed was set to 200 RPM throughout the experiment. Thecontents of the flask were heated at 200° C. for 60 minutes and then thetemperature was gradually increased to 210° C. over 5 minutes. Thereaction mixture was held at 21° C. for 120 minutes and then heated upto 280° C. in 30 minutes. Once at 280° C., vacuum was gradually appliedover the next 5 minutes until the pressure inside the flask reached 100mm of Hg. The pressure inside the flask was further reduced to 0.3 mm ofHg over the next 10 minutes. A pressure of 0.3 mm of Hg was maintainedfor a total time of 90 minutes to remove excess unreacted diols. A highmelt viscosity, visually clear and colorless polymer was obtained with aglass transition temperature of 87.7° C. and an inherent viscosity of0.71 dl/g. NMR analysis showed that the polymer was composed of 19.8 mol% ethylene glycol residues.

Example 1C

This example illustrates the preparation of a copolyester with a targetcomposition of 100 mol % dimethyl terephthalate residues, 20 mol %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues, and 80 mol %1,4-cyclohexanedimethanol residues (31/69 cis/trans).

A mixture of 77.68 g of dimethyl terephthalate, 48.46 g of1,4-cyclohexanedimethanol, 17.86 g of2,2,4,4-tetramethyl-1,3-cyclobutanediol, and 0.046 g of dibutyl tinoxide was placed in a 500-milliliter flask equipped with an inlet fornitrogen, a metal stirrer, and a short distillation column. Thispolyester was prepared in a manner similar to that described in Example1A. A high melt viscosity, visually clear and colorless polymer wasobtained with a glass transition temperature of 100.5° C. and aninherent viscosity of 0.73 dl/g. NMR analysis showed that the polymerwas composed of 80.5 mol % 1,4-cyclohexanedimethanol residues and 19.5mol % 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues.

Example 1D

This example illustrates the preparation of a copolyester with a targetcomposition of 100 mol % dimethyl terephthalate residues, 40 mol %dimethyl isophthalate residues, and 100 mol % 1,4-cyclohexanedimethanolresidues (28/72 cis/trans).

A mixture of 42.83 g of dimethyl terephthalate, 55.26 g of1,4-cyclohexanedimethanol, 28.45 g of dimethyl isophthalate, and 0.0419g of dibutyl tin oxide was placed in a 500-milliliter flask equippedwith an inlet for nitrogen, a metal stirrer, and a short distillationcolumn. The flask was placed in a Wood's metal bath already heated to210° C. The stirring speed was set to 200 RPM throughout the experiment.The contents of the flask were heated at 210° C. for 5 minutes and thenthe temperature was gradually increased to 290° C. over 30 minutes. Thereaction mixture was held at 290° C. for 60 minutes and then vacuum wasgradually applied over the next 5 minutes until the pressure inside theflask reached 100 mm of Hg. The pressure inside the flask was furtherreduced to 0.3 mm of Hg over the next 5 minutes. A pressure of 0.3 mm ofHg was maintained for a total time of 90 minutes to remove excessunreacted diols. A high melt viscosity, visually clear and colorlesspolymer was obtained with a glass transition temperature of 81.2° C. andan inherent viscosity of 0.67 dl/g. NMR analysis showed that the polymerwas composed of 100 mol % 1,4-cyclohexanedimethanol residues and 40.2mol % dimethyl isophthalate residues.

Example 1E

This example illustrates the preparation of a copolyester with a targetcomposition of 100 mol % dimethyl terephthalate residues, 40 mol %ethylene glycol residues, and 60 mol % 1,4-cyclohexanedimethanolresidues (31/69 cis/trans).

A mixture of 81.3 g of dimethyl terephthalate, 42.85 g of1,4-cyclohexanedimethanol, 34.44 g of ethylene glycol, and 0.0419 g ofdibutyl tin oxide was placed in a 500-milliliter flask equipped with aninlet for nitrogen, a metal stirrer, and a short distillation column.The flask was placed in a Wood's metal bath already heated to 200° C.The stirring speed was set to 200 RPM throughout the experiment. Thecontents of the flask were heated at 200° C. for 60 minutes and then thetemperature was gradually increased to 210° C. over 5 minutes. Thereaction mixture was held at 210° C. for 120 minutes and then heated upto 280° C. in 30 minutes. Once at 280° C., vacuum was gradually appliedover the next 5 minutes until the pressure inside the flask reached 100mm of Hg. The pressure inside the flask was further reduced to 0.3 mm ofHg over the next 10 minutes. A pressure of 0.3 mm of Hg was maintainedfor a total time of 90 minutes to remove excess unreacted diols. A highmelt viscosity, visually clear and colorless polymer was obtained with aglass transition temperature of 82.1° C. and an inherent viscosity of0.64 dl/g. NMR analysis showed that the polymer was composed of 34.5 mol% ethylene glycol residues.

Example 1F

This example illustrates the preparation of a copolyester with a targetcomposition of 100 mol % dimethyl terephthalate residues, 40 mol %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues, and 60 mol %1,4-cyclohexanedimethanol residues (31/69 cis/trans).

A mixture of 77.4 g of dimethyl terephthalate, 36.9 g of1,4-cyclohexanedimethanol, 32.5 g of2,2,4,4-tetramethyl-1,3-cyclobutanediol, and 0.046 g of dibutyl tinoxide was placed in a 500-milliliter flask equipped with an inlet fornitrogen, a metal stirrer, and a short distillation column. The flaskwas placed in a Wood's metal bath already heated to 210° C. The stirringspeed was set to 200 RPM throughout the experiment. The contents of theflask were heated at 210° C. for 3 minutes and then the temperature wasgradually increased to 260° C. over 30 minutes. The reaction mixture washeld at 260° C. for 120 minutes and then heated up to 290° C. in 30minutes. Once at 290° C., vacuum was gradually applied over the next 5minutes until the pressure inside the flask reached 100 mm of Hg. Thepressure inside the flask was further reduced to 0.3 mm of Hg over thenext 5 minutes. A pressure of 0.3 mm of Hg was maintained for a totaltime of 90 minutes to remove excess unreacted diols. A high meltviscosity, visually clear and colorless polymer was obtained with aglass transition temperature of 122° C. and an inherent viscosity of0.65 dl/g. NMR analysis showed that the polymer was composed of 59.9 mol% 1,4-cyclohexanedimethanol residues and 40.1 mol %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues.

Example 1G

This example illustrates the preparation of a copolyester with a targetcomposition of 100 mol % dimethyl terephthalate residues, 20 mol %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues (98/2 cis/trans), and80 mol % 1,4-cyclohexanedimethanol residues (31/69 cis/trans).

A mixture of 77.68 g of dimethyl terephthalate, 48.46 g of1,4-cyclohexanedimethanol, 20.77 g of2,2,4,4-tetramethyl-1,3-cyclobutanediol, and 0.046 g of dibutyl tinoxide was placed in a 500-milliliter flask equipped with an inlet fornitrogen, a metal stirrer, and a short distillation column. The flaskwas placed in a Wood's metal bath already heated to 21° C. The stirringspeed was set to 200 RPM throughout the experiment. The contents of theflask were heated at 210° C. for 3 minutes and then the temperature wasgradually increased to 260° C. over 30 minutes. The reaction mixture washeld at 260° C. for 120 minutes and then heated up to 290° C. in 30minutes. Once at 290° C., vacuum was gradually applied over the next 5minutes until the pressure inside the flask reached 100 mm of Hg and thestirring speed was also reduced to 100 RPM. The pressure inside theflask was further reduced to 0.3 mm of Hg over the next 5 minutes andthe stirring speed was reduced to 50 RPM. A pressure of 0.3 mm of Hg wasmaintained for a total time of 60 minutes to remove excess unreacteddiols. A high melt viscosity, visually clear and colorless polymer wasobtained with a glass transition temperature of 103° C. and an inherentviscosity of 0.65 dl/g. NMR analysis showed that the polymer wascomposed of 85.7 mol % 1,4-cyclohexanedimethanol residues and 14.3 mol %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues.

Example 1H

This example illustrates the preparation of a copolyester with a targetcomposition of 100 mol % dimethyl terephthalate residues, 20 mol %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues (5/95 cis/trans), and80 mol % 1,4-cyclohexanedimethanol residues (31/69 cis/trans).

A mixture of 77.68 g of dimethyl terephthalate, 48.46 g of1,4-cyclohexanedimethanol, 20.77 g of2,2,4,4-tetramethyl-1,3-cyclobutanediol, and 0.046 g of dibutyl tinoxide was placed in a 500-milliliter flask equipped with an inlet fornitrogen, a metal stirrer, and a short distillation column. The flaskwas placed in a Wood's metal bath already heated to 210° C. The stirringspeed was set to 200 RPM at the beginning of the experiment. Thecontents of the flask were heated at 210° C. for 3 minutes and then thetemperature was gradually increased to 260° C. over 30 minutes. Thereaction mixture was held at 260° C. for 120 minutes and then heated upto 290° C. in 30 minutes. Once at 290° C., vacuum was gradually appliedover the next 5 minutes with a set point of 100 mm of Hg and thestirring speed was also reduced to 100 RPM. The pressure inside theflask was further reduced to a set point of 0.3 mm of Hg over the next 5minutes and the stirring speed was reduced to 50 RPM. This pressure wasmaintained for a total time of 60 minutes to remove excess unreacteddiols. It was noted that the vacuum system failed to reach the set pointmentioned above, but produced enough vacuum to produce a high meltviscosity, visually clear and colorless polymer with a glass transitiontemperature of 99° C. and an inherent viscosity of 0.73 dl/g. NMRanalysis showed that the polymer was composed of 85 mol %1,4-cyclohexanedimethanol residues and 15 mol %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues.

Example 2

This example illustrates that 2,2,4,4-tetramethyl-1,3-cyclobutanediolimproves the toughness of PCT-based copolyesters (polyesters containingterephthalic acid and 1,4-cyclohexanedimethanol).

Copolyesters based on 2,2,4,4-tetramethyl-1,3-cyclobutanediol wereprepared as described below. The cis/trans ratio of the1,4-cyclohexanedimethanol was approximately 31/69 for all samples.Copolyesters based on ethylene glycol and 1,4-cyclohexanedimethanol werecommercial polyesters. The copolyester of Example 2A (Eastar PCTG 5445)was obtained from Eastman Chemical Co. The copolyester of Example 2B wasobtained from Eastman Chemical Co. under the trade name Spectar. Example2C and Example 2D were prepared on a pilot plant scale (each a 15-lbbatch) following an adaptation of the procedure described in Example 1Aand having the inherent viscosities and glass transition temperaturesdescribed in Table 2 below. Example 2C was prepared with a target tinamount of 300 ppm (Dibutyltin Oxide). The final product contained 295ppm tin. The color values for the polyester of Example 2C were L*=77.11;a*=−1.50; and b*=5.79. Example 2D was prepared with a target tin amountof 300 ppm (Dibutyltin Oxide). The final product contained 307 ppm tin.The color values for the polyester of Example 2D were L*=66.72;a*=−1.22; and b*=16.28.

Materials were injection molded into bars and subsequently notched forIzod testing. The notched Izod impact strengths were obtained as afunction of temperature and are also reported in Table 2.

For a given sample, the Izod impact strength undergoes a majortransition in a short temperature span. For instance, the Izod impactstrength of a copolyester based on 38 mol % ethylene glycol undergoesthis transition between 15 and 20° C. This transition temperature isassociated with a change in failure mode; brittle/low energy failures atlower temperatures and ductile/high energy failures at highertemperatures. The transition temperature is denoted as thebrittle-to-ductile transition temperature, T_(bd), and is a measure oftoughness. T_(bd) is reported in Table 2 and plotted against mol %comonomer in FIG. 2.

The data shows that adding 2,2,4,4-tetramethyl-1,3-cyclobutanediol toPCT lowers T_(bd) and improves the toughness, as compared to ethyleneglycol, which increases T_(bd) of PCT.

TABLE 2 Notched Izod Impact Energy (ft-lb/in) Comonomer IV T_(g) T_(bd)at at at at at at at at at at Example (mol %)¹ (dl/g) (° C.) (° C.) at−20° C. −15° C. −10° C. −5° C. 0° C. 5° C. 10° C. 15° C. 20° C. 25° C.30° C. 2A 38.0% B 0.68 86 18 NA NA NA 1.5 NA NA 1.5 1.5 32   32   NA 2B69.0% B 0.69 82 26 NA NA NA NA NA NA 2.1 NA 2.4 13.7 28.7 2C 22.0% C0.66 106 −5 1.5 NA 12 23   23 NA 23   NA NA NA NA 2D 42.8% C 0.60 133−12 2.5 2.5 11 NA 14 NA NA NA NA NA NA ¹The balance of the glycolcomponent of the polyesters in the Table is 1,4-cyclohexanedimethanol.All polymers were prepared from 100 mole % dimethyl terephthalate. NA =Not available.

where: B is Ethylene glycol

C is 2,2,4,4-Tetramethyl-1,3-cyclobutanediol (50/50 cis/trans)

Example 3

This example illustrates that 2,2,4,4-tetramethyl-1,3-cyclobutanediolcan improve the toughness of PCT-based copolyesters (polyesterscontaining terephthalic acid and 1,4-cyclohexanedimethanol). Polyestersprepared in this example comprise from 15 to 25 mol % of2,2,4,4-tetramethyl-1,3-cyclobutanediol residues.

Copolyesters based on dimethyl terephthalate,2,2,4,4-tetramethyl-1,3-cyclobutanediol, and 1,4-cyclohexanedimethanolwere prepared as described below, having the composition and propertiesshown on Table 3. The balance up to 100 mol % of the diol component ofthe polyesters in Table 3 was 1,4-cyclohexanedimethanol (31/69cis/trans).

Materials were injection molded into both 3.2 mm and 6.4 mm thick barsand subsequently notched for Izod impact testing. The notched Izodimpact strengths were obtained at 23° C. and are reported in Table 3.Density, Tg, and crystallization halftime were measured on the moldedbars. Melt viscosity was measured on pellets at 290° C.

TABLE 3 Compilation of various properties for certain polyesters usefulin the invention Notched Notched Izod of Izod of 3.2 mm 6.4 mm Meltthick thick Crystallization Viscosity Pellet Molded bars at bars atSpecific Halftime from at 1 rad/sec TMCD % cis IV Bar IV 23° C. 23° C.Gravity Tg melt at 170° C. at 290° C. Example mole % TMCD (dl/g) (dl/g)(J/m) (J/m) (g/mL) (° C.) (min) (Poise) A 15 48.8 0.736 0.707 1069 8781.184 104 15 5649 B 18 NA 0.728 0.715 980 1039 1.183 108 22 6621 C 20 NA0.706 0.696 1006 1130 1.182 106 52 6321 D 22 NA 0.732 0.703 959 9881.178 108 63 7161 E 21 NA 0.715 0.692 932 482 1.179 110 56 6162 F 24 NA0.708 0.677 976 812 1.180 109 58 6282 G 23 NA 0.650 0.610 647 270 1.182107 46 3172 H 23 47.9 0.590 0.549 769 274 1.181 106 47 1736 I 23 48.10.531 0.516 696 352 1.182 105 19 1292 J 23 47.8 0.364 NA NA NA NA 98 NA167 NA = Not available.

Example 3A

21.24 lb (49.71 gram-mol) dimethyl terephthalate, 14.34 lb (45.21gram-mol) 1,4-cyclohexanedimethanol, and 4.58 lb (14.44 gram-mol)2,2,4,4-tetramethyl-1,3-cyclobutanediol were reacted together in thepresence of 200 ppm of the catalyst butyltin tris(2-ethylhexanoate). Thereaction was carried out under a nitrogen gas purge in an 18-gallonstainless steel pressure vessel fitted with a condensing column, avacuum system, and a HELICONE-type agitator. With the agitator runningat 25 RPM, the reaction mixture temperature was increased to 250° C. andthe pressure was increased to 20 psig. The reaction mixture was held for2 hours at 250° C. and at a pressure of 20 psig. The pressure was thendecreased to 0 psig at a rate of 3 psig/minute. The temperature of thereaction mixture was then increased to 270° C. and the pressure wasdecreased to 90 mm of Hg. After a 1 hour hold time at 270° C. and 90 mmof Hg, the agitator speed was decreased to 15 RPM, the reaction mixturetemperature was increased to 290° C., and the pressure was decreased to<1 mm of Hg. The reaction mixture was held at 290° C. and at a pressureof <1 mm of Hg until the power draw to the agitator no longer increased(70 minutes). The pressure of the pressure vessel was then increased to1 atmosphere using nitrogen gas. The molten polymer was then extrudedfrom the pressure vessel. The cooled, extruded polymer was ground topass a 6-mm screen. The polymer had an inherent viscosity of 0.736 dL/gand a Tg of 104° C. NMR analysis showed that the polymer was composed of85.4 mol % 1,4-cyclohexane-dimethanol residues and 14.6 mol %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues. The polymer had colorvalues of: L*=78.20, a*=−1.62, and b*=6.23.

Example 3B to Example 3D

The polyesters described in Example 3B to Example 3D were preparedfollowing a procedure similar to the one described for Example 3A. Thecomposition and properties of these polyesters are shown in Table 3.

Example 3E

21.24 lb (49.71 gram-mol) dimethyl terephthalate, 12.61 lb (39.77gram-mol) 1,4-cyclohexanedimethanol, and 6.30 lb (19.88 gram-mol)2,2,4,4-tetramethyl-1,3-cyclobutanediol were reacted together in thepresence of 200 ppm of the catalyst butyltin tris(2-ethylhexanoate). Thereaction was carried out under a nitrogen gas purge in an 18-gallonstainless steel pressure vessel fitted with a condensing column, avacuum system, and a HELICONE-type agitator. With the agitator runningat 25 RPM, the reaction mixture temperature was increased to 250° C. andthe pressure was increased to 20 psig. The reaction mixture was held for2 hours at 250° C. and 20 psig pressure. The pressure was then decreasedto 0 psig at a rate of 3 psig/minute. The temperature of the reactionmixture was then increased to 270° C. and the pressure was decreased to90 mm of Hg. After a 1 hour hold time at 270° C. and 90 mm of Hg, theagitator speed was decreased to 15 RPM, the reaction mixture temperaturewas increased to 290° C., and the pressure was decreased to <1 mm of Hg.The reaction mixture was held at 290° C. and at a pressure of <1 mm ofHg for 60 minutes. The pressure of the pressure vessel was thenincreased to 1 atmosphere using nitrogen gas. The molten polymer wasthen extruded from the pressure vessel. The cooled, extruded polymer wasground to pass a 6-mm screen. The polymer had an inherent viscosity of0.715 dL/g and a Tg of 110° C. X-ray analysis showed that the polyesterhad 223 ppm tin. NMR analysis showed that the polymer was composed of78.6 mol % 1,4-cyclohexane-dimethanol residues and 21.4 mol %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues. The polymer had colorvalues of: L*=76.45, a*=−1.65, and b*=6.47.

Example 3F

The polyester described in Example 3F was prepared following a proceduresimilar to the one described for Example 3A. The composition andproperties of this polyester are shown in Table 3.

Example 3H

21.24 lb (49.71 gram-mol) dimethyl terephthalate, 12.61 lb (39.77gram-mol) 1,4-cyclohexanedimethanol, and 6.30 lb (19.88 gram-mol)2,2,4,4-tetramethyl-1,3-cyclobutanediol were reacted together in thepresence of 200 ppm of the catalyst butyltin tris(2-ethylhexanoate). Thereaction was carried out under a nitrogen gas purge in an 18-gallonstainless steel pressure vessel fitted with a condensing column, avacuum system, and a HELICONE-type agitator. With the agitator runningat 25 RPM, the reaction mixture temperature was increased to 250° C. andthe pressure was increased to 20 psig. The reaction mixture was held for2 hours at 250° C. and 20 psig pressure. The pressure was then decreasedto 0 psig at a rate of 3 psig/minute. The temperature of the reactionmixture was then increased to 270° C. and the pressure was decreased to90 mm of Hg. After a 1 hour hold time at 270° C. and 90 mm of Hg, theagitator speed was decreased to 15 RPM, the reaction mixture temperaturewas increased to 290° C., and the pressure was decreased to <1 mm of Hg.The reaction mixture was held at 290° C. and at a pressure of <1 mm ofHg for 12 minutes. The pressure of the pressure vessel was thenincreased to 1 atmosphere using nitrogen gas. The molten polymer wasthen extruded from the pressure vessel. The cooled, extruded polymer wasground to pass a 6-mm screen. The polymer had an inherent viscosity of0.590 dL/g and a Tg of 106° C. NMR analysis showed that the polymer wascomposed of 77.1 mol % 1,4-cyclohexane-dimethanol residues and 22.9 mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues. The polymer hadcolor values of: L*=83.27, a*=−1.34, and b*=5.08.

Example 31

21.24 lb (49.71 gram-mol) dimethyl terephthalate, 12.61 lb (39.77gram-mol) 1,4-cyclohexanedimethanol, and 6.30 lb (19.88 gram-mol)2,2,4,4-tetramethyl-1,3-cyclobutanediol were reacted together in thepresence of 200 ppm of the catalyst butyltin tris(2-ethylhexanoate). Thereaction was carried out under a nitrogen gas purge in an 18-gallonstainless steel pressure vessel fitted with a condensing column, avacuum system, and a HELICONE-type agitator. With the agitator runningat 25 RPM, the reaction mixture temperature was increased to 250° C. andthe pressure was increased to 20 psig. The reaction mixture was held for2 hours at 250° C. and 20 psig pressure. The pressure was then decreasedto 0 psig at a rate of 3 psig/minute. The temperature of the reactionmixture was then increased to 270° C. and the pressure was decreased to90 mm of Hg. After a 1 hour hold time at 270° C. and 90 mm of Hg, theagitator speed was decreased to 15 RPM, the reaction mixture temperaturewas increased to 290° C., and the pressure was decreased to 4 mm of Hg.The reaction mixture was held at 290° C. and at a pressure of 4 mm of Hgfor 30 minutes. The pressure of the pressure vessel was then increasedto 1 atmosphere using nitrogen gas. The molten polymer was then extrudedfrom the pressure vessel. The cooled, extruded polymer was ground topass a 6-mm screen. The polymer had an inherent viscosity of 0.531 dL/gand a Tg of 105° C. NMR analysis showed that the polymer was composed of76.9 mol % 1,4-cyclohexane-dimethanol residues and 23.1 mol %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues. The polymer had colorvalues of: L*=80.42, a*=−1.28, and b*=5.13.

Example 3J

21.24 lb (49.71 gram-mol) dimethyl terephthalate, 12.61 lb (39.77gram-mol) 1,4-cyclohexanedimethanol, and 6.30 lb (19.88 gram-mol)2,2,4,4-tetramethyl-1,3-cyclobutanediol were reacted together in thepresence of 200 ppm of the catalyst butyltin tris(2-ethylhexanoate). Thereaction was carried out under a nitrogen gas purge in an 18-gallonstainless steel pressure vessel fitted with a condensing column, avacuum system, and a HELICONE-type agitator. With the agitator runningat 25 RPM, the reaction mixture temperature was increased to 250° C. andthe pressure was increased to 20 psig. The reaction mixture was held for2 hours at 250° C. and 20 psig pressure. The pressure was then decreasedto 0 psig at a rate of 3 psig/minute. The temperature of the reactionmixture was then increased to 270° C. and the pressure was decreased to90 mm of Hg. After a 1 hour hold time at 270° C. and 90 mm of Hg, theagitator speed was decreased to 15 RPM, the reaction mixture temperaturewas increased to 290° C., and the pressure was decreased to 4 mm of Hg.When the reaction mixture temperature was 290° C. and the pressure was 4mm of Hg, the pressure of the pressure vessel was immediately increasedto 1 atmosphere using nitrogen gas. The molten polymer was then extrudedfrom the pressure vessel. The cooled, extruded polymer was ground topass a 6-mm screen. The polymer had an inherent viscosity of 0.364 dL/gand a Tg of 98° C. NMR analysis showed that the polymer was composed of77.5 mol % 1,4-cyclohexane-dimethanol residues and 22.5 mol %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues. The polymer had colorvalues of: L*=77.20, a*=−1.47, and b*=4.62.

Example 4

This example illustrates that 2,2,4,4-tetramethyl-1,3-cyclobutanediolcan improve the toughness of PCT-based copolyesters (polyesterscontaining terephthalic acid and 1,4-cyclohexanedimethanol). Polyestersprepared in this example fall comprise more than 25 to less than 40 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues.

Copolyesters based on dimethyl terephthalate,2,2,4,4-tetramethyl-1,3-cyclobutanediol, and 1,4-cyclohexanedimethanol(31/69 cis/trans) were prepared as described below, having thecomposition and properties shown on Table 4. The balance up to 100 mol %of the diol component of the polyesters in Table 4 was1,4-cyclohexanedimethanol (31/69 cis/trans).

Materials were injection molded into both 3.2 mm and 6.4 mm thick barsand subsequently notched for Izod impact testing. The notched Izodimpact strengths were obtained at 23° C. and are reported in Table 4.Density, Tg, and crystallization halftime were measured on the moldedbars. Melt viscosity was measured on pellets at 290° C.

TABLE 4 Compilation of various properties for certain polyesters usefulin the invention Notched Notched Izod of Izod of 3.2 mm 6.4 mm Meltthick thick Crystallization Viscosity Pellet Molded bars at bars atSpecific Halftime from at 1 rad/sec TMCD % cis IV Bar IV 23° C. 23° C.Gravity Tg melt at 170° C. at 290° C. Example mole % TMCD (dl/g) (dl/g)(J/m) (J/m) (g/mL) (° C.) (min) (Poise) A 27 47.8 0.714 0.678 877 8781.178 113 280 8312 B 31 NA 0.667 0.641 807 789 1.174 116 600 6592 NA =Not available.

Example 4A

21.24 lb (49.71 gram-mol) dimethyl terephthalate, 11.82 lb (37.28gram-mol) 1,4-cyclohexanedimethanol, and 6.90 lb (21.77 gram-mol)2,2,4,4-tetramethyl-1,3-cyclobutanediol were reacted together in thepresence of 200 ppm of the catalyst butyltin tris(2-ethylhexanoate). Thereaction was carried out under a nitrogen gas purge in an 18-gallonstainless steel pressure vessel fitted with a condensing column, avacuum system, and a HELICONE-type agitator. With the agitator runningat 25 RPM, the reaction mixture temperature was increased to 250° C. andthe pressure was increased to 20 psig. The reaction mixture was held for2 hours at 250° C. and 20 psig pressure. The pressure was then decreasedto 0 psig at a rate of 3 psig/minute. The temperature of the reactionmixture was then increased to 270° C. and the pressure was decreased to90 mm of Hg. After a 1 hour hold time at 270° C. and 90 mm of Hg, theagitator speed was decreased to 15 RPM, the reaction mixture temperaturewas increased to 290° C., and the pressure was decreased to <1 mm of Hg.The reaction mixture was held at 290° C. and at a pressure of <1 mm ofHg until the power draw to the agitator no longer increased (50minutes). The pressure of the pressure vessel was then increased to 1atmosphere using nitrogen gas. The molten polymer was then extruded fromthe pressure vessel. The cooled, extruded polymer was ground to pass a6-mm screen. The polymer had an inherent viscosity of 0.714 dL/g and aTg of 113° C. NMR analysis showed that the polymer was composed of 73.3mol % 1,4-cyclohexane-dimethanol residues and 26.7 mol %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues.

Example 4B

The polyester of Example 4B was prepared following a procedure similarto the one described for Example 4A. The composition and properties ofthis polyester are shown in Table 4.

Example 5

This example illustrates that 2,2,4,4-tetramethyl-1,3-cyclobutanediolcan improve the toughness of PCT-based copolyesters (polyesterscontaining terephthalic acid and 1,4-cyclohexanedimethanol).

A copolyester based on dimethyl terephthalate,2,2,4,4-tetramethyl-1,3-cyclobutanediol, and 1,4-cyclohexanedimethanolwas prepared as described below, having the composition and propertiesshown on Table 5. The balance up to 100 mol % of the diol component ofthe polyesters in Table 5 was 1,4-cyclohexanedimethanol (31/69cis/trans).

The polyester was injection molded into both 3.2 mm and 6.4 mm thickbars and subsequently notched for Izod impact testing. The notched Izodimpact strengths were obtained at 23° C. and are reported in Table 5.Density, Tg, and crystallization halftime were measured on the moldedbars. Melt viscosity was measured on pellets at 290° C.

TABLE 5 Compilation of various properties for certain polyesters usefulin the invention Notched Notched Izod of Izod of 3.2 mm 6.4 mm Meltthick thick Crystallization Viscosity Pellet Molded bars at bars atSpecific Halftime from at 1 rad/sec TMCD % cis IV Bar IV 23° C. 23° C.Gravity Tg melt at 170° C. at 290° C. Example mole % TMCD (dl/g) (dl/g)(J/m) (J/m) (g/mL) (° C.) (min) (Poise) A 44 46.2 0.657 0.626 727 7341.172 119 NA 9751 NA = Not available

Example 5A

21.24 lb (49.71 gram-mol) dimethyl terephthalate, 8.84 lb (27.88gram-mol) 1,4-cyclohexanedimethanol, and 10.08 lb (31.77 gram-mol)2,2,4,4-tetramethyl-1,3-cyclobutanediol were reacted together in thepresence of 200 ppm of the catalyst butyltin tris(2-ethylhexanoate). Thereaction was carried out under a nitrogen gas purge in an 18-gallonstainless steel pressure vessel fitted with a condensing column, avacuum system, and a HELICONE-type agitator. With the agitator runningat 25 RPM, the reaction mixture temperature was increased to 250° C. andthe pressure was increased to 20 psig. The reaction mixture was held for2 hours at 250° C. and 20 psig pressure. The pressure was then decreasedto 0 psig at a rate of 3 psig/minute. Then the agitator speed wasdecreased to 15 RPM, the temperature of the reaction mixture was thenincreased to 290° C. and the pressure was decreased to 2 mm of Hg. Thereaction mixture was held at 290° C. and at a pressure of 2 mm of Hguntil the power draw to the agitator no longer increased (80 minutes).The pressure of the pressure vessel was then increased to 1 atmosphereusing nitrogen gas. The molten polymer was then extruded from thepressure vessel. The cooled, extruded polymer was ground to pass a 6-mmscreen. The polymer had an inherent viscosity of 0.657 dL/g and a Tg of119° C. NMR analysis showed that the polymer was composed of 56.3 mol %1,4-cyclohexane-dimethanol residues and 43.7 mol %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues. The polymer had colorvalues of: L*=75.04, a*=−1.82, and b*=6.72.

Example 6 Comparative Example

This example shows data for comparative materials are shown in Table 6.The PC was Makrolon 2608 from Bayer, with a nominal composition of 100mole % bisphenol A residues and 100 mole % diphenyl carbonate residues.Makrolon 2608 has a nominal melt flow rate of 20 grams/10 minutesmeasured at 30° C. using a 1.2 kg weight. The PET was Eastar 9921 fromEastman Chemical Company, with a nominal composition of 100 mole %terephthalic acid, 3.5 mole % cyclohexanedimethanol (CHDM) and 96.5 mole% ethylene glycol. The PETG was Eastar 6763 from Eastman ChemicalCompany, with a nominal composition of 100 mole % terephthalic acid, 31mole % cyclohexanedimethanol (CHDM) and 69 mole % ethylene glycol. ThePCTG was Eastar DN001 from Eastman Chemical Company, with a nominalcomposition of 100 mole % terephthalic acid, 62 mole %cyclohexanedimethanol (CHDM) and 38 mole % ethylene glycol. The PCTA wasEastar AN001 from Eastman Chemical Company, with a nominal compositionof 65 mole % terephthalic acid, 35 mole % isophthalic acid and 100 mole% cyclohexanedimethanol (CHDM). The Polysulfone was Udel 1700 fromSolvay, with a nominal composition of 100 mole % bisphenol A residuesand 100 mole % 4,4-dichlorosulfonyl sulfone residues. Udel 1700 has anominal melt flow rate of 6.5 grams/10 minutes measured at 343C using a2.16 kg weight. The SAN was Lustran 31 from Lanxess, with a nominalcomposition of 76 weight % styrene and 24 weight % acrylonitrile.Lustran 31 has a nominal melt flow rate of 7.5 grams/10 minutes measuredat 23° C. using a 3.8 kg weight. The examples of the invention showimproved toughness in 6.4 mm thickness bars compared to all of the otherresins.

TABLE 6 Compilation of various properties for certain commercialpolymers Notched Notched Izod of Izod of 3.2 mm 6.4 mm CrystallizationMolded thick bars thick bars Specific Halftime from Polymer Pellet IVBar IV at 23° C. at 23° C. Gravity Tg melt Example name (dl/g) (dl/g)(J/m) (J/m) (g/mL) (° C.) (min) A PC  12 MFR NA 929  108  1.20 146 NA BPCTG 0.73 0.696 NB 70 1.23 87  30 at 170° C. C PCTA 0.72 0.702 98 591.20 87  15 at 150° C. D PETG 0.75 0.692 83 59 1.27 80 2500 at 130° C. EPET 0.76 0.726 45 48 1.33 78   1.5 at 170° C. F SAN 7.5 MFR NA 21 NA1.07 ~110 NA G PSU 6.5 MFR NA 69 NA 1.24 ~190 NA NA = Not available

Example 7

This example illustrates the effect of the amount of2,2,4,4-tetramethyl-1,3-cyclobutanediol used for the preparation of thepolyesters of the invention on the glass transition temperature of thepolyesters. Polyesters prepared in this example comprise from 15 to 25mol % of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues.

Example 7A to Example 7G

Dimethyl terephthalate, 1,4-cyclohexanedimethanol, and2,2,4,4-tetramethyl-1,3-cyclobutanediol were weighed into a 500-mlsingle neck round bottom flask. NMR analysis on the2,2,4,4-tetramethyl-1,3-cyclobutanediol starting material showed acis/trans ratio of 53/47. The polyesters of this example were preparedwith a 1.2/1 glycol/acid ratio with the entire excess coming from the2,2,4,4-tetramethyl-1,3-cyclobutanediol. Enough dibutyltin oxidecatalyst was added to give 300 ppm tin in the final polymer. The flaskwas under a 0.2 SCFC nitrogen purge with vacuum reduction capability.The flask was immersed in a Belmont metal bath at 200° C. and stirred at200 RPM after the reactants had melted. After about 2.5 hours, thetemperature was raised to 210° C. and these conditions were held for anadditional 2 hours. The temperature was raised to 285° C. (inapproximately 25 minutes) and the pressure was reduced to 0.3 mm of Hgover a period of 5 minutes. The stirring was reduced as the viscosityincreased, with 15 RPM being the minimum stirring used. The totalpolymerization time was varied to attain the target inherentviscosities. After the polymerization was complete, the Belmont metalbath was lowered and the polymer was allowed to cool to below its glasstransition temperature. After about 30 minutes, the flask was reimmersedin the Belmont metal bath (the temperature had been increased to 295° C.during this 30 minute wait) and the polymer mass was heated until itpulled away from the glass flask. The polymer mass was stirred at midlevel in the flask until the polymer had cooled. The polymer was removedfrom the flask and ground to pass a 3 mm screen. Variations to thisprocedure were made to produce the copolyesters described below with atargeted composition of 20 mol %.

Inherent viscosities were measured as described in the “MeasurementMethods” section above. The compositions of the polyesters weredetermined by ¹H NMR as explained before in the Measurement Methodssection. The glass transition temperatures were determined by DSC, usingthe second heat after quench at a rate of 20° C./min.

Example 7H to Example 7Q

These polyesters were prepared by carrying out the ester exchange andpolycondensation reactions in separate stages. The ester exchangeexperiments were conducted in a continuous temperature rise (CTR)reactor. The CTR was a 3000 ml glass reactor equipped with a singleshaft impeller blade agitator, covered with an electric heating mantleand fitted with a heated packed reflux condenser column. The reactor wascharged with 777 g (4 moles) of dimethyl terephthalate, 230 g (1.6moles) of 2,2,4,4-tetramethyl-1,3,-cyclobutanediol, 460.8 g (3.2 moles)of cyclohexane dimethanol and 1.12 g of butyltin tris-2-ethylhexanoate(such that there will be 200 ppm tin metal in the final polymer). Theheating mantle was set manually to 100% output. The set points and datacollection were facilitated by a Camile process control system. Once thereactants were melted, stirring was initiated and slowly increased to250 rpm. The temperature of the reactor gradually increased with runtime. The weight of methanol collected was recorded via balance. Thereaction was stopped when methanol evolution stopped or at apre-selected lower temperature of 260° C. The oligomer was dischargedwith a nitrogen purge and cooled to room temperature. The oligomer wasfrozen with liquid nitrogen and broken into pieces small enough to beweighed into a 500 ml round bottom flask.

In the polycondensation reactions, a 500 ml round bottom flask wascharged with approximately 150 g of the oligomer prepared above. Theflask was equipped with a stainless steel stirrer and polymer head. Theglassware was set up on a half mole polymer rig and the Camile sequencewas initiated. The stirrer was positioned one full turn from the flaskbottom once the oligomer melted. The temperature/pressure/stir ratesequence controlled by the Camile software for each example is reportedin the following tables.

Time Temp Vacuum Stir Stage (min) (° C.) (torr) (rpm) Camile Sequencefor Example 7H and Example 7I 1 5 245 760 0 2 5 245 760 50 3 30 265 76050 4 3 265 90 50 5 110 290 90 50 6 5 290 6 25 7 110 290 6 25 CamileSequence for Example 7N to Example 7Q 1 5 245 760 0 2 5 245 760 50 3 30265 760 50 4 3 265 90 50 5 110 290 90 50 6 5 290 3 25 7 110 290 3 25Camile Sequence for Example 7K and Example 7L 1 5 245 760 0 2 5 245 76050 3 30 265 760 50 4 3 265 90 50 5 110 290 90 50 6 5 290 2 25 7 110 2902 25 Camile Sequence for Example 7J and Example 7M 1 5 245 760 0 2 5 245760 50 3 30 265 760 50 4 3 265 90 50 5 110 290 90 50 6 5 290 1 25 7 110290 1 25

The resulting polymers were recovered from the flask, chopped using ahydraulic chopper, and ground to a 6 mm screen size. Samples of eachground polymer were submitted for inherent viscosity in 60/40 (wt/wt)phenol/tetrachloroethane at a concentration of 0.5 g/100 ml at 25° C.,catalyst level (Sn) by x-ray fluorescence, and color (L*, a*, b*) bytransmission spectroscopy. Polymer composition was obtained by ¹H NMR.Samples were submitted for thermal stability and melt viscosity testingusing a Rheometrics Mechanical Spectrometer (RMS-800).

The table below shows the experimental data for the polyesters of thisexample. The data shows that an increase in the level of2,2,4,4-tetramethyl-1,3-cyclobutanediol raises the glass transitiontemperature in an almost linear fashion, for a constant inherentviscosity. FIG. 3 also shows the dependence of Tg on composition andinherent viscosity.

TABLE 7 Glass transition temperature as a function of inherent viscosityand composition η_(o) at η_(o) at η_(o) at Exam- mol % % cis IV T_(g)260° C. 275° C. 290° C. ple TMCD TMCD (dL/g) (° C.) (Poise) (Poise)(Poise) A 20 51.4 0.72 109 11356 19503 5527 B 19.1 51.4 0.60 106 68913937 2051 C 19 53.2 0.64 107 8072 4745 2686 D 18.8 54.4 0.70 108 149378774 4610 E 17.8 52.4 0.50 103 3563 1225 883 F 17.5 51.9 0.75 107 2116010877 5256 G 17.5 52 0.42 98 NA NA NA H 22.8 53.5 0.69 109 NA NA NA I22.7 52.2 0.68 108 NA NA NA J 23.4 52.4 0.73 111 NA NA NA K 23.3 52.90.71 111 NA NA NA L 23.3 52.4 0.74 112 NA NA NA M 23.2 52.5 0.74 112 NANA NA N 23.1 52.5 0.71 111 NA NA NA O 22.8 52.4 0.73 112 NA NA NA P 22.753 0.69 112 NA NA NA Q 22.7 52 0.70 111 NA NA NA NA = Not available

Example 8

This example illustrates the effect of the amount of2,2,4,4-tetramethyl-1,3-cyclobutanediol used for the preparation of thepolyesters of the invention on the glass transition temperature of thepolyesters. Polyesters prepared in this example fall comprise more than25 to less than 40 mol % of 2,2,4,4-tetramethyl-1,3-cyclobutanediolresidues.

Dimethyl terephthalate, 1,4-cyclohexanedimethanol, and2,2,4,4-tetramethyl-1,3-cyclobutanediol were weighed into a 500-mlsingle neck round bottom flask. NMR analysis on the2,2,4,4-tetramethyl-1,3-cyclobutanediol starting material showed acis/trans ratio of 53/47. The polyesters of this example were preparedwith a 1.2/1 glycol/acid ratio with the entire excess coming from the2,2,4,4-tetramethyl-1,3-cyclobutanediol. Enough dibutyltin oxidecatalyst was added to give 300 ppm tin in the final polymer. The flaskwas under a 0.2 SCFC nitrogen purge with vacuum reduction capability.The flask was immersed in a Belmont metal bath at 200° C. and stirred at200 RPM after the reactants had melted. After about 2.5 hours, thetemperature was raised to 210° C. and these conditions were held for anadditional 2 hours. The temperature was raised to 285° C. (inapproximately 25 minutes) and the pressure was reduced to 0.3 mm of Hgover a period of 5 minutes. The stirring was reduced as the viscosityincreased, with 15 RPM being the minimum stirring used. The totalpolymerization time was varied to attain the target inherentviscosities. After the polymerization was complete, the Belmont metalbath was lowered and the polymer was allowed to cool to below its glasstransition temperature. After about 30 minutes, the flask was reimmersedin the Belmont metal bath (the temperature had been increased to 295° C.during this 30 minute wait) and the polymer mass was heated until itpulled away from the glass flask. The polymer mass was stirred at midlevel in the flask until the polymer had cooled. The polymer was removedfrom the flask and ground to pass a 3 mm screen. Variations to thisprocedure were made to produce the copolyesters described below with atargeted composition of 32 mol %.

Inherent viscosities were measured as described in the “MeasurementMethods” section above. The compositions of the polyesters weredetermined by ¹H NMR as explained before in the Measurement Methodssection. The glass transition temperatures were determined by DSC, usingthe second heat after quench at a rate of 20° C./min.

The table below shows the experimental data for the polyesters of thisexample. FIG. 3 also shows the dependence of Tg on composition andinherent viscosity. The data shows that an increase in the level of2,2,4,4-tetramethyl-1,3-cyclobutanediol raises the glass transitiontemperature in an almost linear fashion, for a constant inherentviscosity.

TABLE 8 Glass transition temperature as a function of inherent viscosityand composition η_(o) at η_(o) at η_(o) at Exam- mol % % cis IV T_(g)260° C. 275° C. 290° C. ple TMCD TMCD (dL/g) (° C.) (Poise) (Poise)(Poise) A 32.2 51.9 0.71 118 29685 16074 8522 B 31.6 51.5 0.55 112 51952899 2088 C 31.5 50.8 0.62 112 8192 4133 2258 D 30.7 50.7 0.54 111 43452434 1154 E 30.3 51.2 0.61 111 7929 4383 2261 F 30.0 51.4 0.74 117 3147617864 8630 G 29.0 51.5 0.67 112 16322 8787 4355 H 31.1 51.4 0.35 102 NANA NA NA = Not available

Example 9

This example illustrates the effect of the amount of2,2,4,4-tetramethyl-1,3-cyclobutanediol used for the preparation of thepolyesters of the invention on the glass transition temperature of thepolyesters. Polyesters prepared in this example comprise2,2,4,4-tetramethyl-1,3-cyclobutanediol residues in an amount of 40 mol% or greater.

Examples A to C

These polyesters were prepared by carrying out the ester exchange andpolycondensation reactions in separate stages. The ester exchangeexperiments were conducted in a continuous temperature rise (CTR)reactor. The CTR was a 3000 ml glass reactor equipped with a singleshaft impeller blade agitator, covered with an electric heating mantleand fitted with a heated packed reflux condenser column. The reactor wascharged with 777 g of dimethyl terephthalate, 375 g of2,2,4,4-tetramethyl-1,3,-cyclobutanediol, 317 g of cyclohexanedimethanol and 1.12 g of butyltin tris-2-ethylhexanoate (such that therewill be 200 ppm tin metal in the final polymer). The heating mantle wasset manually to 100% output. The set points and data collection werefacilitated by a Camile process control system. Once the reactants weremelted, stirring was initiated and slowly increased to 250 rpm. Thetemperature of the reactor gradually increased with run time. The weightof methanol collected was recorded via balance. The reaction was stoppedwhen methanol evolution stopped or at a pre-selected lower temperatureof 260° C. The oligomer was discharged with a nitrogen purge and cooledto room temperature. The oligomer was frozen with liquid nitrogen andbroken into pieces small enough to be weighed into a 500 ml round bottomflask.

In the polycondensation reactions, a 500 ml round bottom flask wascharged with 150 g of the oligomer prepared above. The flask wasequipped with a stainless steel stirrer and polymer head. The glasswarewas set up on a half mole polymer, rig and the Camile sequence wasinitiated. The stirrer was positioned one full turn from the flaskbottom once the oligomer melted. The temperature/pressure/stir ratesequence controlled by the Camile software for these examples isreported in the following table, unless otherwise specified below.

Vacuum Stage Time (min) Temp (° C.) (torr) Stir (rpm) Camile Sequencefor Polycondensation Reactions 1 5 245 760 0 2 5 245 760 50 3 30 265 76050 4 3 265 90 50 5 110 290 90 50 6 5 290 6 25 7 110 290 6 25 CamileSequence for Examples A and B 1 5 245 760 0 2 5 245 760 50 3 30 265 76050 4 3 265 90 50 5 110 290 90 50 6 5 290 6 25 7 80 290 6 25

For Example C, the same sequence in the preceding table was used, exceptthe time was 50 min in Stage 7.

The resulting polymers were recovered from the flask, chopped using ahydraulic chopper, and ground to a 6 mm screen size. Samples of eachground polymer were submitted for inherent viscosity in 60/40 (wt/wt)phenol/tetrachloroethane at a concentration of 0.5 g/100 ml at 25° C.,catalyst level (Sn) by x-ray fluorescence, and color (L*, a*, b*) bytransmission spectroscopy. Polymer composition was obtained by ¹H NMR.Samples were submitted for thermal stability and melt viscosity testingusing a Rheometrics Mechanical Spectrometer (RMS-800).

Examples D to K and M

The polyesters of these examples were prepared as described above forExamples A to C, except that the target tin amount in the final polymerwas 150 ppm for examples AD to K and M. The following tables describethe temperature/pressure/stir rate sequences controlled by the Camilesoftware for these examples.

Camile Sequence for Examples D, F, and H Vacuum Stage Time (min) Temp (°C.) (torr) Stir (rpm) 1 5 245 760 0 2 5 245 760 50 3 30 265 760 50 4 3265 400 50 5 110 290 400 50 6 5 290 8 50 7 110 295 8 50

For Example D, the stirrer was turned to 25 rpm with 95 min left inStage 7.

Camile Sequence for Example E Vacuum Stage Time (min) Temp (° C.) (torr)Stir (rpm) 1 10 245 760 0 2 5 245 760 50 3 30 283 760 50 4 3 283 175 505 5 283 5 50 6 5 283 1.2 50 7 71 285 1.2 50

For Example K, the same sequence in the preceding table was used, exceptthe time was 75 min in Stage 7.

Vacuum Stage Time (min) Temp (° C.) (torr) Stir (rpm) Camile Sequencefor Example G 1 10 245 760 0 2 5 245 760 50 3 30 285 760 50 4 3 285 17550 5 5 285 5 50 6 5 285 4 50 7 220 290 4 50 Camile Sequence for ExampleI 1 5 245 760 0 2 5 245 760 50 3 30 265 760 50 4 3 265 90 50 5 110 28590 50 6 5 285 6 50 7 70 290 6 50 Camile Sequence for Example J 1 5 245760 0 2 5 245 760 50 3 30 265 760 50 4 3 265 90 50 5 110 290 90 50 6 5290 6 25 7 110 295 6 25

Examples L and K

Dimethyl terephthalate, 1,4-cyclohexanedimethanol, and2,2,4,4-tetramethyl-1,3-cyclobutanediol were weighed into a 500-mlsingle neck round bottom flask. The polyesters of this example wereprepared with a 1.2/1 glycol/acid ratio with the entire excess comingfrom the 2,2,4,4-tetramethyl-1,3-cyclobutanediol. Enough dibutyltinoxide catalyst was added to give 300 ppm tin in the final polymer. Theflask was under a 0.2 SCFC nitrogen purge with vacuum reductioncapability. The flask was immersed in a Belmont metal bath at 200° C.and stirred at 200 RPM after the reactants had melted. After about 2.5hours, the temperature was raised to 21° C. and these conditions wereheld for an additional 2 hours. The temperature was raised to 285° C.(in approximately 25 minutes) and the pressure was reduced to 0.3 mm ofHg over a period of 5 minutes. The stirring was reduced as the viscosityincreased, with 15 RPM being the minimum stirring used. The totalpolymerization time was varied to attain the target inherentviscosities. After the polymerization was complete, the Belmont metalbath was lowered and the polymer was allowed to cool to below its glasstransition temperature. After about 30 minutes, the flask was reimmersedin the Belmont metal bath (the temperature had been increased to 295° C.during this 30 minute wait) and the polymer mass was heated until itpulled away from the glass flask. The polymer mass was stirred at midlevel in the flask until the polymer had cooled. The polymer was removedfrom the flask and ground to pass a 3 mm screen. Variations to thisprocedure were made to produce the copolyesters described below with atargeted composition of 45 mol %.

Inherent viscosities were measured as described in the “MeasurementMethods” section above. The compositions of the polyesters weredetermined by ¹H NMR as explained before in the Measurement Methodssection. The glass transition temperatures were determined by DSC, usingthe second heat after quench at a rate of 20° C./min.

The table below shows the experimental data for the polyesters of thisexample. The data shows that an increase in the level of2,2,4,4-tetramethyl-1,3-cyclobutanediol raises the glass transitiontemperature in an almost linear fashion, for a constant inherentviscosity. FIG. 3 also shows the dependence of Tg on composition andinherent viscosity.

TABLE 9 Glass transition temperature as a function of inherent viscosityand composition η_(o) at η_(o) at η_(o) at Exam- mol % % cis IV T_(g)260° C. 275° C. 290° C. ple TMCD TMCD (dL/g) (° C.) (Poise) (Poise)(Poise) A 44.2 36.4 0.49 118 NA NA NA B 44.3 36.3 0.51 119 NA NA NA C44.4 35.6 0.55 118 NA NA NA D 46.3 52.4 0.52 NA NA NA NA E 45.7 50.90.54 NA NA NA NA F 46.3 52.6 0.56 NA NA NA NA G 46 50.6 0.56 NA NA NA NAH 46.5 51.8 0.57 NA NA NA NA I 45.6 51.2 0.58 NA NA NA NA J 46 51.9 0.58NA NA NA NA K 45.5 51.2 0.59 NA NA NA NA L 46.1 49.6 0.383 117 NA NA 387K 45.6 50.5 0.325 108 NA NA NA M 47.2 NA 0.48 NA NA NA NA NA = Notavailable

Example 10

This example illustrates the effect of the predominance of the type of2,2,4,4-tetramethyl-1,3-cyclobutanediol isomer (cis or trans) on theglass transition temperature of the polyester.

Dimethyl terephthalate, 1,4-cyclohexanedimethanol, and2,2,4,4-tetramethyl-1,3-cyclobutanediol were weighed into a 500-mlsingle neck round bottom flask. The polyesters of this example wereprepared with a 1.2/1 glycol/acid ratio with the entire excess comingfrom the 2,2,4,4-tetramethyl-1,3-cyclobutanediol. Enough dibutyltinoxide catalyst was added to give 300 ppm tin in the final polymer. Theflask was under a 0.2 SCFC nitrogen purge with vacuum reductioncapability. The flask was immersed in a Belmont metal bath at 200° C.and stirred at 200 RPM after the reactants had melted. After about 2.5hours, the temperature was raised to 210° C. and these conditions wereheld for an additional 2 hours. The temperature was raised to 285° C.(in approximately 25 minutes) and the pressure was reduced to 0.3 mm ofHg over a period of 5 minutes. The stirring was reduced as the viscosityincreased, with 15 RPM being the minimum stirring used. The totalpolymerization time was varied to attain the target inherentviscosities. After the polymerization was complete, the Belmont metalbath was lowered and the polymer was allowed to cool to below its glasstransition temperature. After about 30 minutes, the flask was reimmersedin the Belmont metal bath (the temperature had been increased to 295° C.during this 30 minute wait) and the polymer mass was heated until itpulled away from the glass flask. The polymer mass was stirred at midlevel in the flask until the polymer had cooled. The polymer was removedfrom the flask and ground to pass a 3 mm screen. Variations to thisprocedure were made to produce the copolyesters described below with atargeted composition of 45 mol %.

Inherent viscosities were measured as described in the “MeasurementMethods” section above. The compositions of the polyesters weredetermined by ¹H NMR as explained before in the Measurement Methodssection. The glass transition temperatures were determined by DSC, usingthe second heat after quench at a rate of 20° C./min.

The table below shows the experimental data for the polyesters of thisExample. The data shows that cis 2,2,4,4-tetramethyl-1,3-cyclobutanediolis approximately twice as effective as trans2,2,4,4-tetramethyl-1,3-cyclobutanediol at increasing the glasstransition temperature for a constant inherent viscosity.

TABLE 10 Effect of 2,2,4,4-tetramethyl-1,3-cyclobutanediol cis/transcomposition on T_(g) η_(o) at η_(o) □at η_(o) at Exam- mol % IV T_(g)260° C. 275° C. 290° C. % cis ple TMCD (dL/g) (° C.) (Poise) (Poise)(Poise) TMCD A 45.8 0.71 119 N.A. N.A. N.A. 4.1 B 43.2 0.72 122 N.A.N.A. N.A. 22.0 C 46.8 0.57 119 26306 16941 6601 22.8 D 43.0 0.67 12555060 36747 14410 23.8 E 43.8 0.72 127 101000 62750 25330 24.5 F 45.90.533 119 11474 6864 2806 26.4 G 45.0 0.35 107 N.A. N.A. N.A. 27.2 H41.2 0.38 106 1214 757 N.A. 29.0 I 44.7 0.59 123 N.A. N.A. N.A. 35.4 J44.4 0.55 118 N.A. N.A. N.A. 35.6 K 44.3 0.51 119 N.A. N.A. N.A. 36.3 L44.0 0.49 128 N.A. N.A. N.A. 71.7 M 43.6 0.52 128 N.A. N.A. N.A. 72.1 N43.6 0.54 127 N.A. N.A. N.A. 72.3 O 41.5 0.58 133 15419 10253 4252 88.7P 43.8 0.57 135 16219 10226 4235 89.6 Q 41.0 0.33 120 521 351 2261 90.4R 43.0 0.56 134 N.A. N.A. N.A. 90.6 S 43.0 0.49 132 7055 4620 2120 90.6T 43.1 0.55 134 12970 8443 3531 91.2 U 45.9 0.52 137 N.A. N.A. N.A. 98.1NA = not available

Example 11 Comparative Example

This example illustrates that a polyester based on 100%2,2,4,4-tetramethyl-1,3-cyclobutanediol has a slow crystallizationhalf-time.

A polyester based solely on terephthalic acid and2,2,4,4-tetramethyl-1,3-cyclobutanediol was prepared in a method similarto the method described in Example 1A with the properties shown on Table11. This polyester was made with 300 ppm dibutyl tin oxide. Thetrans/cis ratio of the 2,2,4,4-tetramethyl-1,3-cyclobutanediol was65/35.

Films were pressed from the ground polymer at 320° C. Crystallizationhalf-time measurements from the melt were made at temperatures from 220to 250° C. at 110° C. increments and are reported in Table 11. Thefastest crystallization half-time for the sample was taken as theminimum value of crystallization half-time as a function of temperature.The fastest crystallization half-time of this polyester is around 1300minutes. This value contrasts with the fact that the polyester (PCT)based solely on terephthalic acid and 1,4-cyclohexanedimethanol (nocomonomer modification) has an extremely short crystallization half-time(<1 min) as shown in FIG. 1.

TABLE 11 Crystallization Half-times (min) at at at at Comonomer 220° C.230° C. 240° C. 250° C. (mol %) IV (dl/g) T_(g) (° C.) T_(max) (° C.)(min) (min) (min) (min) 100 mol % F 0.63 170.0 330 3291 3066 1303 1888where: F is 2,2,4,4-Tetramethyl-1,3-cyclobutanediol (65/35 Trans/Cis)

Example 12

Sheets comprising a polyester that had been prepared with a targetcomposition of 100 mole % terephthalic acid residues, 80 mole %1,4-cyclohexanedimethanol residues, and 20 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues were produced using a3.5 inch single screw extruder. A sheet was extruded continuously,gauged to a thickness of 177 mil and then various sheets were sheared tosize. Inherent viscosity and glass transition temperature were measuredon one sheet. The sheet inherent viscosity was measured to be 0.69 dl/g.The glass transition temperature of the sheet was measured to be 106° C.Sheets were then conditioned at 50% relative humidity and 60° C. for 2weeks. Sheets were subsequently thermoformed into a female mold having adraw ratio of 2.5:1 using a Brown thermoforming machine. Thethermoforming oven heaters were set to 70/60/60% output using top heatonly. Sheets were left in the oven for various amounts of time in orderto determine the effect of sheet temperature on the part quality asshown in the table below. Part quality was determined by measuring thevolume of the thermoformed part, calculating the draw, and visuallyinspecting the thermoformed part. The draw was calculated as the partvolume divided by the maximum part volume achieved in this set ofexperiments (Example G). The thermoformed part was visually inspectedfor any blisters and the degree of blistering rated as none (N), low(L), or high (H). The results below demonstrate that these thermoplasticsheets with a glass transition temperature of 106° C. can bethermoformed under the conditions shown below, as evidenced by thesesheets having at least 95% draw and no blistering, without predrying thesheets prior to thermoforming.

Thermoforming Conditions Part Quality Sheet Part Heat Time TemperatureVolume Blisters Example (s) (° C.) (mL) Draw (%) (N, L, H) A 86 145 50164 N B 100 150 500 63 N C 118 156 672 85 N D 135 163 736 94 N E 143 166760 97 N F 150 168 740 94 L G 159 172 787 100 L

Example 13

Sheets comprising a polyester that had been prepared with a targetcomposition of 100 mole % terephthalic acid residues, 80 mole %1,4-cyclohexanedimethanol residues, and 20 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues were produced using a3.5 inch single screw. A sheet was extruded continuously, gauged to athickness of 177 mil and then various sheets were sheared to size.Inherent viscosity and glass transition temperature were measured on onesheet. The sheet inherent viscosity was measured to be 0.69 dl/g. Theglass transition temperature of the sheet was measured to be 106° C.Sheets were then conditioned at 100% relative humidity and 25° C. for 2weeks. Sheets were subsequently thermoformed into a female mold having adraw ratio of 2.5:1 using a Brown thermoforming machine. Thethermoforming oven heaters were set to 60/40/40% output using top heatonly. Sheets were left in the oven for various amounts of time in orderto determine the effect of sheet temperature on the part quality asshown in the table below. Part quality was determined by measuring thevolume of the thermoformed part, calculating the draw, and visuallyinspecting the thermoformed part. The draw was calculated as the partvolume divided by the maximum part volume achieved in this set ofexperiments (Example G). The thermoformed part was visually inspectedfor any blisters and the degree of blistering rated as none (N), low(L), or high (H). The results below demonstrate that these thermoplasticsheets with a glass transition temperature of 106° C. can bethermoformed under the conditions shown below, as evidenced by theproduction of sheets having at least 95% draw and no blistering, withoutpredrying the sheets prior to thermoforming.

Thermoforming Conditions Part Quality Sheet Part Heat Time TemperatureVolume Blisters Example (s) (° C.) (mL) Draw (%) (N, L, H) A 141 154 39453 N B 163 157 606 82 N C 185 160 702 95 N D 195 161 698 95 N E 215 163699 95 L F 230 168 705 96 L G 274 174 737 100 H H 275 181 726 99 H

Example 14 Comparative Example

Sheets consisting of Kelvx 201 were produced using a 3.5 inch singlescrew extruder. Kelvx is a blend consisting of 69.85% PCTG (Eastar fromEastman Chemical Co. having 100 mole % terephthalic acid residues, 62mole % 1,4-cyclohexanedimethanol residues, and 38 mole % ethylene glycolresidues); 30% PC (bisphenol A polycarbonate); and 0.15% Weston 619(stabilizer sold by Crompton Corporation). A sheet was extrudedcontinuously, gauged to a thickness of 177 mil and then various sheetswere sheared to size. The glass transition temperature was measured onone sheet and was 100° C. Sheets were then conditioned at 50% relativehumidity and 60° C. for 2 weeks. Sheets were subsequently thermoformedinto a female mold having a draw ratio of 2.5:1 using a Brownthermoforming machine. The thermoforming oven heaters were set to70/60/60% output using top heat only. Sheets were left in the oven forvarious amounts of time in order to determine the effect of sheettemperature on the part quality as shown in the table below. Partquality was determined by measuring the volume of the thermoformed part,calculating the draw, and visually inspecting the thermoformed part. Thedraw was calculated as the part volume divided by the maximum partvolume achieved in this set of experiments (Example E). The thermoformedpart was visually inspected for any blisters and the degree ofblistering rated as none (N), low (L), or high (H). The results belowdemonstrate that these thermoplastic sheets with a glass transitiontemperature of 100° C. can be thermoformed under the conditions shownbelow, as evidenced by the production of sheets having at least 95% drawand no blistering, without predrying the sheets prior to thermoforming.

Thermoforming Conditions Part Quality Sheet Part Heat Time TemperatureVolume Blisters Example (s) (° C.) (mL) Draw (%) (N, L, H) A 90 146 58275 N B 101 150 644 83 N C 111 154 763 98 N D 126 159 733 95 N E 126 159775 100 N F 141 165 757 98 N G 148 168 760 98 L

Example 15 Comparative Example

Sheets consisting of Kelvx 201 were produced using a 3.5 inch singlescrew extruder. A sheet was extruded continuously, gauged to a thicknessof 177 mil and then various sheets were sheared to size. The glasstransition temperature was measured on one sheet and was 100° C. Sheetswere then conditioned at 100% relative humidity and 25° C. for 2 weeks.Sheets were subsequently thermoformed into a female mold having a drawratio of 2.5:1 using a Brown thermoforming machine. The thermoformingoven heaters were set to 60/40/40% output using top heat only. Sheetswere left in the oven for various amounts of time in order to determinethe effect of sheet temperature on the part quality as shown in thetable below. Part quality was determined by measuring the volume of thethermoformed part, calculating the draw, and visually inspecting thethermoformed part. The draw was calculated as the part volume divided bythe maximum part volume achieved in this set of experiments (Example H).The thermoformed part was visually inspected for any blisters and thedegree of blistering rated as none (N), low (L), or high (H). Theresults below demonstrate that these thermoplastic sheets with a glasstransition temperature of 100° C. can be thermoformed under theconditions shown below, as evidenced by the production of sheets havinggreater than 95% draw and no blistering, without predrying the sheetsprior to thermoforming.

Thermoforming Conditions Part Quality Sheet Part Heat Time TemperatureVolume Blisters Example (s) (° C.) (mL) Draw (%) (N, L, H) A 110 143 18525 N B 145 149 529 70 N C 170 154 721 95 N D 175 156 725 96 N E 185 157728 96 N F 206 160 743 98 L G 253 NR 742 98 H H 261 166 756 100 H NR =Not recorded

Example 16 Comparative Example

Sheets consisting of PCTG 25976 (100 mole % terephthalic acid residues,62 mole % 1,4-cyclohexanedimethanol residues, and 38 mole % ethyleneglycol residues) were produced using a 3.5 inch single screw extruder. Asheet was extruded continuously, gauged to a thickness of 118 mil andthen various sheets were sheared to size. The glass transitiontemperature was measured on one sheet and was 87° C. Sheets were thenconditioned at 50% relative humidity and 60° C. for 4 weeks. Themoisture level was measured to be 0.17 wt %. Sheets were subsequentlythermoformed into a female mold having a draw ratio of 2.5:1 using aBrown thermoforming machine. The thermoforming oven heaters were set to70/60/60% output using top heat only. Sheets were left in the oven forvarious amounts of time in order to determine the effect of sheettemperature on the part quality as shown in the table below. Partquality was determined by measuring the volume of the thermoformed part,calculating the draw, and visually inspecting the thermoformed part. Thedraw was calculated as the part volume divided by the maximum partvolume achieved in this set of experiments (Example A). The thermoformedpart was visually inspected for any blisters and the degree ofblistering rated as none (N), low (L), or high (H). The results belowdemonstrate that these thermoplastic sheets with a glass transitiontemperature of 87° C. can be thermoformed under the conditions shownbelow, as evidenced by the production of sheets having greater than 95%draw and no blistering, without predrying the sheets prior tothermoforming.

Thermoforming Conditions Part Quality Sheet Part Heat Time TemperatureVolume Blisters Example (s) (° C.) (mL) Draw (%) (N, L, H) A 102 183 816100 N B 92 171 811 99 N C 77 160 805 99 N D 68 149 804 99 N E 55 143 79097 N F 57 138 697 85 N

Example 17 Comparative Example

A miscible blend consisting of 20 wt % Teijin L-1250 polycarbonate (abisphenol-A polycarbonate), 79.85 wt % PCTG 25976, and 0.15 wt % Weston619 was produced using a 1.25 inch single screw extruder. Sheetsconsisting of the blend were then produced using a 3.5 inch single screwextruder. A sheet was extruded continuously, gauged to a thickness of118 mil and then various sheets were sheared to size. The glasstransition temperature was measured on one sheet and was 94° C. Sheetswere then conditioned at 50% relative humidity and 60° C. for 4 weeks.The moisture level was measured to be 0.25 wt %. Sheets weresubsequently thermoformed into a female mold having a draw ratio of2.5:1 using a Brown thermoforming machine. The thermoforming ovenheaters were set to 70/60/60% output using top heat only. Sheets wereleft in the oven for various amounts of time in order to determine theeffect of sheet temperature on the part quality as shown in the tablebelow. Part quality was determined by measuring the volume of thethermoformed part, calculating the draw, and visually inspecting thethermoformed part. The draw was calculated as the part volume divided bythe maximum part volume achieved in this set of experiments (Example A).The thermoformed part was visually inspected for any blisters and thedegree of blistering rated as none (N), low (L), or high (H). Theresults below demonstrate that these thermoplastic sheets with a glasstransition temperature of 94° C. can be thermoformed under theconditions shown below, as evidenced by the production of sheets havinggreater than 95% draw and no blistering, without predrying the sheetsprior to thermoforming.

Thermoforming Conditions Part Quality Sheet Part Heat Time TemperatureVolume Blisters Example (s) (° C.) (mL) Draw (%) (N, L, H) A 92 184 844100 H B 86 171 838 99 N C 73 160 834 99 N D 58 143 787 93 N E 55 143 66579 N

Example 18 Comparative Example

A miscible blend consisting of 30 wt % Teijin L-1250 polycarbonate,69.85 wt % PCTG 25976, and 0.15 wt % Weston 619 was produced using a1.25 inch single screw extruder. Sheets consisting of the blend werethen produced using a 3.5 inch single screw extruder. A sheet wasextruded continuously, gauged to a thickness of 118 mil and then varioussheets were sheared to size. The glass transition temperature wasmeasured on one sheet and was 99° C. Sheets were then conditioned at 50%relative humidity and 60° C. for 4 weeks. The moisture level wasmeasured to be 0.25 wt %. Sheets were subsequently thermoformed into afemale mold having a draw ratio of 2.5:1 using a Brown thermoformingmachine. The thermoforming oven heaters were set to 70/60/60% outputusing top heat only. Sheets were left in the oven for various amounts oftime in order to determine the effect of sheet temperature on the partquality as shown in the table below. Part quality was determined bymeasuring the volume of the thermoformed part, calculating the draw, andvisually inspecting the thermoformed part. The draw was calculated asthe part volume divided by the maximum part volume achieved in this setof experiments (Example A). The thermoformed part was visually inspectedfor any blisters and the degree of blistering rated as none (N), low(L), or high (H). The results below demonstrate that these thermoplasticsheets with a glass transition temperature of 99° C. can be thermoformedunder the conditions shown below, as evidenced by the production ofsheets having greater than 95% draw and no blistering, without predryingthe sheets prior to thermoforming.

Thermoforming Conditions Part Quality Sheet Part Heat Time TemperatureVolume Blisters Example (s) (° C.) (mL) Draw (%) (N, L, H) A 128 194 854100 H B 98 182 831 97 L C 79 160 821 96 N D 71 149 819 96 N E 55 145 78592 N F 46 143 0 0 NA G 36 132 0 0 NA NA = not applicable. A value ofzero indicates that the sheet was not formed because it did not pullinto the mold (likely because it was too cold).

Example 19 Comparative Example

A miscible blend consisting of 40 wt % Teijin L-1250 polycarbonate,59.85 wt % PCTG 25976, and 0.15 wt % Weston 619 was produced using a1.25 inch single screw extruder. Sheets consisting of the blend werethen produced using a 3.5 inch single screw extruder. A sheet wasextruded continuously, gauged to a thickness of 118 mil and then varioussheets were sheared to size. The glass transition temperature wasmeasured on one sheet and was 105° C. Sheets were then conditioned at50% relative humidity and 60° C. for 4 weeks. The moisture level wasmeasured to be 0.265 wt %. Sheets were subsequently thermoformed into afemale mold having a draw ratio of 2.5:1 using a Brown thermoformingmachine. The thermoforming oven heaters were set to 70/60/60% outputusing top heat only. Sheets were left in the oven for various amounts oftime in order to determine the effect of sheet temperature on the partquality as shown in the table below. Part quality was determined bymeasuring the volume of the thermoformed part, calculating the draw, andvisually inspecting the thermoformed part. The draw was calculated asthe part volume divided by the maximum part volume achieved in this setof experiments (Examples 8A to 8E). The thermoformed part was visuallyinspected for any blisters and the degree of blistering rated as none(N), low (L), or high (H). The results below demonstrate that thesethermoplastic sheets with a glass transition temperature of 105° C. canbe thermoformed under the conditions shown below, as evidenced by theproduction of sheets having greater than 95% draw and no blistering,without predrying the sheets prior to thermoforming.

Thermoforming Conditions Part Quality Sheet Part Heat Time TemperatureVolume Blisters Example (s) (° C.) (mL) Draw (%) (N, L, H) A 111 191 828100 H B 104 182 828 100 H C 99 179 827 100 N D 97 177 827 100 N E 78 160826 100 N F 68 149 759 92 N G 65 143 606 73 N

Example 20 Comparative Example

A miscible blend consisting of 50 wt % Teijin L-1250 polycarbonate,49.85 wt % PCTG 25976, and 0.15 wt % Weston 619 was produced using a1.25 inch single screw extruder. A sheet was extruded continuously,gauged to a thickness of 118 mil and then various sheets were sheared tosize. The glass transition temperature was measured on one sheet and was111° C. Sheets were then conditioned at 50% relative humidity and 60° C.for 4 weeks. The moisture level was measured to be 0.225 wt %. Sheetswere subsequently thermoformed into a female mold having a draw ratio of2.5:1 using a Brown thermoforming machine. The thermoforming ovenheaters were set to 70/60/60% output using top heat only. Sheets wereleft in the oven for various amounts of time in order to determine theeffect of sheet temperature on the part quality as shown in the tablebelow. Part quality was determined by measuring the volume of thethermoformed part, calculating the draw, and visually inspecting thethermoformed part. The draw was calculated as the part volume divided bythe maximum part volume achieved in this set of experiments (Examples Ato D). The thermoformed part was visually inspected for any blisters andthe degree of blistering rated as none (N), low (L), or high (H). Theresults below demonstrate that these thermoplastic sheets with a glasstransition temperature of 111° C. can be thermoformed under theconditions shown below, as evidenced by the production of sheets havinggreater than 95% draw and no blistering, without predrying the sheetsprior to thermoforming.

Thermoforming Conditions Part Quality Sheet Part Heat Time TemperatureVolume Blisters Example (s) (° C.) (mL) Draw (%) (N, L, H) A 118 192 815100 H B 99 182 815 100 H C 97 177 814 100 L D 87 171 813 100 N E 80 160802 98 N F 64 154 739 91 N G 60 149 0 0 NA NA = not applicable. A valueof zero indicates that the sheet was not formed because it did not pullinto the mold (likely because it was too cold).

Example 21 Comparative Example

A miscible blend consisting of 60 wt % Teijin L-1250 polycarbonate,39.85 wt % PCTG 25976, and 0.15 wt % Weston 619 was produced using a1.25 inch single screw extruder. Sheets consisting of the blend werethen produced using a 3.5 inch single screw extruder. A sheet wasextruded continuously, gauged to a thickness of 118 mil and then varioussheets were sheared to size. The glass transition temperature wasmeasured on one sheet and was 117° C. Sheets were then conditioned at50% relative humidity and 60° C. for 4 weeks. The moisture level wasmeasured to be 0.215 wt %. Sheets were subsequently thermoformed into afemale mold having a draw ratio of 2.5:1 using a Brown thermoformingmachine. The thermoforming oven heaters were set to 70/60/60% outputusing top heat only. Sheets were left in the oven for various amounts oftime in order to determine the effect of sheet temperature on the partquality as shown in the table below. Part quality was determined bymeasuring the volume of the thermoformed part, calculating the draw, andvisually inspecting the thermoformed part. The draw was calculated asthe part volume divided by the maximum part volume achieved in this setof experiments (Example A). The thermoformed part was visually inspectedfor any blisters and the degree of blistering rated as none (N), low(L), or high (H). The results below demonstrate that these thermoplasticsheets with a glass transition temperature of 117° C. cannot bethermoformed under the conditions shown below, as evidenced by theinability to produce sheets having greater than 95% draw and noblistering, without predrying the sheets prior to thermoforming.

Thermoforming Conditions Part Quality Sheet Part Heat Time TemperatureVolume Blisters Example (s) (° C.) (mL) Draw (%) (N, L, H) A 114 196 813100 H B 100 182 804 99 H C 99 177 801 98 L D 92 171 784 96 L E 82 168727 89 L F 87 166 597 73 N

Example 22 Comparative Example

A miscible blend consisting of 65 wt % Teijin L-1250 polycarbonate,34.85 wt % PCTG 25976, and 0.15 wt % Weston 619 was produced using a1.25 inch single screw extruder. Sheets consisting of the blend werethen produced using a 3.5 inch single screw extruder. A sheet wasextruded continuously, gauged to a thickness of 118 mil and then varioussheets were sheared to size. The glass transition temperature wasmeasured on one sheet and was 120° C. Sheets were then conditioned at50% relative humidity and 60° C. for 4 weeks. The moisture level wasmeasured to be 0.23 wt %. Sheets were subsequently thermoformed into afemale mold having a draw ratio of 2.5:1 using a Brown thermoformingmachine. The thermoforming oven heaters were set to 70/60/60% outputusing top heat only. Sheets were left in the oven for various amounts oftime in order to determine the effect of sheet temperature on the partquality as shown in the table below. Part quality was determined bymeasuring the volume of the thermoformed part, calculating the draw, andvisually inspecting the thermoformed part. The draw was calculated asthe part volume divided by the maximum part volume achieved in this setof experiments (Example A). The thermoformed part was visually inspectedfor any blisters and the degree of blistering rated as none (N), low(L), or high (H). The results below demonstrate that these thermoplasticsheets with a glass transition temperature of 120° C. cannot bethermoformed under the conditions shown below, as evidenced by theinability to produce sheets having greater than 95% draw and noblistering, without predrying the sheets prior to thermoforming.

Thermoforming Conditions Part Quality Sheet Part Heat Time TemperatureVolume Blisters Example (s) (° C.) (mL) Draw (%) (N, L, H) A 120 197 825100 H B 101 177 820 99 H C 95 174 781 95 L D 85 171 727 88 L E 83 166558 68 L

Example 23 Comparative Example

A miscible blend consisting of 70 wt % Teijin L-1250 polycarbonate,29.85 wt % PCTG 25976, and 0.15 wt % Weston 619 was produced using a1.25 inch single screw extruder. Sheets consisting of the blend werethen produced using a 3.5 inch single screw extruder. A sheet wasextruded continuously, gauged to a thickness of 118 mil and then varioussheets were sheared to size. The glass transition temperature wasmeasured on one sheet and was 123° C. Sheets were then conditioned at50% relative humidity and 60° C. for 4 weeks. The moisture level wasmeasured to be 0.205 wt %. Sheets were subsequently thermoformed into afemale mold having a draw ratio of 2.5:1 using a Brown thermoformingmachine. The thermoforming oven heaters were set to 70/60/60% outputusing top heat only. Sheets were left in the oven for various amounts oftime in order to determine the effect of sheet temperature on the partquality as shown in the table below. Part quality was determined bymeasuring the volume of the thermoformed part, calculating the draw, andvisually inspecting the thermoformed part. The draw was calculated asthe part volume divided by the maximum part volume achieved in this setof experiments (Examples A and B). The thermoformed part was visuallyinspected for any blisters and the degree of blistering rated as none(N), low (L), or high (H). The results below demonstrate that thesethermoplastic sheets with a glass transition temperature of 123° C.cannot be thermoformed under the conditions shown below, as evidenced bythe inability to produce sheets having greater than 95% draw and noblistering, without predrying the sheets prior to thermoforming.

Thermoforming Conditions Part Quality Sheet Part Heat Time TemperatureVolume Blisters Example (s) (° C.) (mL) Draw (%) (N, L, H) A 126 198 826100 H B 111 188 822 100 H C 97 177 787 95 L D 74 166 161 19 L E 58 154 00 NA F 48 149 0 0 NA NA = not applicable. A value of zero indicates thatthe sheet was not formed because it did not pull into the mold (likelybecause it was too cold).

Example 24 Comparative Example

Sheets consisting of Teijin L-1250 polycarbonate were produced using a3.5 inch single screw extruder. A sheet was extruded continuously,gauged to a thickness of 118 mil and then various sheets were sheared tosize. The glass transition temperature was measured on one sheet and was149° C. Sheets were then conditioned at 50% relative humidity and 60° C.for 4 weeks. The moisture level was measured to be 0.16 wt %. Sheetswere subsequently thermoformed into a female mold having a draw ratio of2.5:1 using a Brown thermoforming machine. The thermoforming ovenheaters were set to 70/60/60% output using top heat only. Sheets wereleft in the oven for various amounts of time in order to determine theeffect of sheet temperature on the part quality as shown in the tablebelow. Part quality was determined by measuring the volume of thethermoformed part, calculating the draw and visually inspecting thethermoformed part. The draw was calculated as the part volume divided bythe maximum part volume achieved in this set of experiments (Example A).The thermoformed part was visually inspected for any blisters and thedegree of blistering rated as none (N), low (L), or high (H). Theresults below demonstrate that these thermoplastic sheets with a glasstransition temperature of 149° C. cannot be thermoformed under theconditions shown below, as evidenced by the inability to produce sheetshaving greater than 95% draw and no blistering, without predrying thesheets prior to thermoforming.

Thermoforming Conditions Part Quality Sheet Part Heat Time TemperatureVolume Blisters Example (s) (° C.) (mL) Draw (%) (N, L, H) A 152 216 820100 H B 123 193 805 98 H C 113 191 179 22 H D 106 188 0 0 H E 95 182 0 0NA F 90 171 0 0 NA NA = not applicable. A value of zero indicates thatthe sheet was not formed because it did not pull into the mold (likelybecause it was too cold).

Example 25

This example illustrates the preparation of polyesters comprising atleast one thermal stabilizer, reaction products thereof, and mixturesthereof, resulting in improved stability of the polyester melts duringprocessing.

A variety of polyesters were prepared as described below from 100 mole %dimethyl terephthalate (DMT), 1,4-cyclohexanedimethanol (CHDM), and2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD). The mole % of TMCD forthe experiments of this example is reported in Table 12 below, with theglycol balance being CHDM. The DMT was purchased from Cape Industries,the CHDM (min. 98%) and the TMCD (min. 98%) were from Eastman ChemicalCompany. The tin compound was either dimethyltin oxide (from StremChemical Co. or Gelest, Inc.) or butyltin-tris-2-ethylhexonate (fromAldrich or Arkema). The phosphorus compound was triphenyl phosphate(TPP, from Aldrich (98%) or FERRO, Corp.). Unless otherwise indicatedbelow, the source of phosphorous was added upfront, with the rest of thepolyester reagents. The cis/trans ratio of the CHDM was as describedabove while the cis/trans ratio of the TMCD is reported in Table 12.

TABLE 12 Composition and inherent viscosity for the polyesters ofExample 25 P Sn/P Final Melt TMCD (ppm) actual Pz IV (mole TMCD Sn theo/wt Temp Example (dL/g) %) % cis (ppm) meas ratio (° C.) A 0.605 44.850.0 205¹ none * 290 B 0.583 44.4 51.9 201¹ none * 290 C 0.578 43.9 50.7199¹ none * 290 D 0.607 44.9 50.5 199² none * 290 E 0.437 44.5 52.0 200²none * 290 F 0.585 45.1 50.2 191² 10/11 17.4 290 G 0.580 45.1 50.5 192¹10/11 17.5 290 H 0.541 44.0 52.3 202² 19/20 10.1 290 I 0.595 45.3 50.6198² 20/20 9.9 290 J 0.632 45.6 49.0 203² 20/22 9.2 265 K 0.577 46.250.1 196² 30/26 7.5 265 L 0.608 46.0 49.6 190¹ 20/19 10.0 265 M 0.51745.2 49.4 100² 10/10 10.0 265 N 0.602 46.1 49.2 102² 10/10 10.2 265¹butyltin tris-2-ethylhexanoate was used as the source of tin ²dimethyltin oxide was used as the source of tin

The data in Table 13 shows that the stability of polymer melts forComparative Examples A to D was not deemed acceptable if the sameconditions were to be used at a pilot-pant or commercial scale. Incontrast, experiments having appropriate ratios of tin/phosphorousproduced stable melts, suitable for scale up processes.

TABLE 13 Properties of the polyesters of Example 25 Visual Melt levelPolymer color % foam in grading of Example L* a* b* stabilityobservations polyester polyester A 82.50 −0.89 4.66 4 Yellow tint 34% 4B 79.74 −0.75 4.89 4 Yellow tint 21% 4 C 78.64 −0.39 6.83 4Brownish-yellow 37% 4 tint D 85.44 −1.45 4.07 3 Slight yellow tint 27% 4E 86.19 −1.04 3.94 3 Good color: No 35% 4 yellow tint F 80.92 −1.02 3.222 Good color: No 20% 3 yellow tint G 82.10 −1.67 3.69 2 Good color: No22% 3 yellow tint H 85.74 −0.81 2.46 1 NM NM NM I 82.51 −1.03 2.56 1Good color: No 15% 2 yellow tint J 85.54 −1.07 2.06 1 Good color: No 22%3 yellow tint K 84.54 −0.71 1.07 1 Good color: No 14% 2 yellow tint L85.03 −0.82 1.17 1 Slight yellow tint 14% 3 M 85.02 −0.87 1.59 1 Slightyellow tint 17% 2 N 82.49 −0.86 1.09 1 Good color: No 17% 2 yellow tintO NA NA NA NA NA 35% NA P NA NA NA NA NA  9% NA NM = not measured

The melt level stability reported in Table 13 is based on the followingscale:

1 Stable melt levels, limited off-gassing, similar to conventionalpolyesters where excess glycols slowly boil off 2 Relatively stable meltlevels but some additional void/bubbles compared to 1 above. 3 Unstablemelt levels during vacuum levels, heavy foaming and frothing leading tohigh void volumes (bubbles that increase melt overall volume), unstableoff-gassing, melt level surges that were kept from overflowing flaskonly with adjustment of stirring rate or by having stirrer above levelof melt to push down and break up the foam. Too unstable to scale updependably. 4 Very unstable melt levels during vacuum levels, excessivefoaming and frothing leading to high void volumes (bubbles that increasemelt overall volume), unstable off-gassing, melt level surges thatoverflowed out of flask and frequently pushed melt/foam into the gasspace in vacuum system. Frequently, it was not possible to complete run(greater than 50% of duplicate runs could not be completed for thislevel of stability).

The visual grading reported in Table 13 is based on the following scale:

Grading Explanation 1 Few bubbles: can see through molten polymer 2Sparse bubbles: enough bubbles to obstruct view through polymer but notenough to drastically increase the polymer volume 3 Numerous bubbles:volume of polymer is affected by the bubbles 4 Very dense foam: volumeof polymer is drastically affected by the numerous bubbles

Example 25O and Example 25P are comparative examples. Example 25Orepresents a polyester prepared in a similar manner to pilot plantexamples described below with no phosphorus thermal stabilizer, havingan IV of 0.54 dL/g and containing 100 mole % terephthalic acid residues,43.8 mole % TMCD residues and 56.2 mole % CHDM acid residues. Thispolyester was prepared using butyltin tris-2-ethylhexanoate was used asthe source of tin catalyst (Sn=216 ppm) at 290° C. final finishertemperature and having color values L*=60.97, b*=9.02, and a*=−0.89.Example 25P represents a commercial Kelvx polymer containing 65 mole %terephthalic acid residues, 35 mole % isophthalic acid residues, and 100mole % 1,4-cyclohexanedimethanol residues.

The polyesters of this example were prepared in a 500 ml round bottomflask fitted with a stirrer and a polymer head that allowed both anitrogen purge and vacuum when necessary. Raw materials were weighedinto the flask for a 0.4 mole run (polymer repeat unit=274 grams/mole):0.400 moles of DMT (77.6 grams), 0.224 moles of CHDM (32.3 grams) and0.256 moles of TMCD (36.8 grams) and 0.112 g butyltintris-2-ethylhexanoate or 0.0314 g dimethyl tin oxide (as reported inTable 12), such that there was approximately 200 ppm tin metal in thefinal polymer, but were modified accordingly for other targetconcentrations, such as 100 ppm Sn.

The glycol/acid ratio was 1.2/1 with the excess being 2% CHDM and therest of the 20% excess being TMCD. The catalyst was weighed into theflask, either as a solid or liquid. Triphenyl phosphate was weighed intothe flask as a solid in the amount recited in Table 12 for eachexperiment. 100 ppm (0.0109 g as a liquid) of tetramethyl ammoniumhydroxide (TMAH) was used in the preparation of Example 25K.

The set points and data collection were facilitated by a Camile processcontrol system. Once the reactants were melted, stirring was initiatedand slowly increased as indicated below in the corresponding Camilesequences. The temperature of the reactor also gradually increased withrun time.

The ester exchange and polycondensation reactions were carried out inthe same 500 ml flask. The blade of the stirrer was moved up to the topof the melt during the processing of the polyesters of Example 25A andExample 25B to beat down the foam layer. The temperature/pressure/stirrate sequence controlled by the Camile software for each example isreported in the following tables. The final polymerization temperature(Pz Temp.) for the experiments of this Example ranged from 265° C. to290° C. and is reported in Table 12.

Camile Sequence for Example 25A to Example 25I Temperature Stage Time(minutes) (° C.) Vacuum (torr) Stirring (RPM) 1 3 200 760 0 2 0.1 200760 25 3 2 200 760 25 4 0.1 200 760 100 5 1 200 760 100 6 0.1 200 760200 7 90 200 760 200 8 0.1 210 760 200 9 120 210 760 200 10 5 245 760 5011 5 245 760 50 12 30 265 760 50 13 3 265 90 50 14 110 290 90 50 15 5290 6 25 16 110 290 6 25 17 2 290 400 0 18 1 300 760 0 Temperature,Stage Time (minutes) C. Vacuum (torr) Stirring (RPM) Camile Sequence forExample 25J to Example 25L 1 3 200 760 0 2 0.1 200 760 25 3 2 200 760 254 0.1 200 760 100 5 1 200 760 100 6 0.1 200 760 200 7 90 200 760 200 80.1 210 760 200 9 120 210 760 200 10 5 245 760 50 11 3 245 375 50 12 30245 375 50 13 3 250 20 50 14 30 250 20 50 15 3 255 5 25 16 110 255 5 2517 3 265 1 25 18 110 265 1 25 19 2 265 400 0 20 1 265 760 0 CamileSequence for Example 25M Viscosity constrained sequence, low vacuum 1 3200 760 0 2 0.1 200 760 25 3 2 200 760 25 4 0.1 200 760 100 5 1 200 760100 6 0.1 200 760 200 7 90 200 760 200 8 0.1 210 760 200 9 120 210 760200 10 5 245 760 50 11 3 245 375 50 12 30 245 375 50 13 3 250 20 50 1430 250 20 50 15 3 255 5 25 16 110 255 5 25 17 3 265 0.2 25 18 110 2650.2 25 19 2 265 400 0 20 1 265 760 0 Camile Sequence for Example 25NViscosity constrained sequence, low vacuum 1 3 200 760 0 2 0.1 200 76025 3 2 200 760 25 4 0.1 200 760 100 5 1 200 760 100 6 0.1 200 760 200 790 200 760 200 8 0.1 210 760 200 9 120 210 760 200 10 5 245 760 50 11 3245 375 50 12 30 245 375 50 13 3 250 20 50 14 30 250 20 50 15 3 255 3 2516 110 255 3 25 17 3 265 0.2 25 18 110 265 0.2 25 19 2 265 400 0 20 1265 760 0

Example 26

This example illustrates the preparation of polyesters comprising atleast one thermal stabilizer, reaction products thereof, and mixturesthereof, employing different process conditions from Example 25,resulting in improved stability of the polyester melts duringprocessing.

A variety of polyesters were prepared as described below from 100 mole %DMT, CHDM, and TMCD. The mole % of TMCD for the experiments of thisexample is reported in Table 14 below, with the glycol balance beingCHDM. The DMT, CHDM, and TMCD were of the same origin as in Example 25.The catalyst was dimethyltin oxide (Strem Chemical Co., Batch B4058112),butyltin-tris-2-ethylhexonate (Aldrich, Batch 06423CD, or Arkema), ordibutyl tin oxide (Arkema). The thermal stabilizer was triphenylphosphate, also with the same origin as in Example 25. Unless otherwiseindicated below, the source of phosphorous was added upfront, with therest of the polyester reagents. The cis/trans ratio of the CHDM was asdescribed above while the cis/trans ratio of the TMCD is reported inTable 14. The polyesters of Example 26A and Example 26E were notprepared with TPP.

TABLE 14 Composition and inherent viscosity for the polyesters ofExample 26 P Sn/P Final Melt TMCD (ppm) actual Pz IV (mole TMCD Sn theo/wt Temp Example (dL/g) %) % cis (ppm) meas ratio (° C.) A 0.548 46.350.1 190³ none * 290 B 0.696 45.3 49.3 193² 10/9  21.4 275 C 0.597 45.150.4 199² 20/18 11.1 275 D 0.547 45.6 50.4 195² 30/27 7.2 275 E 0.71445.4 49.9 198² none * 265 F 0.731 44.5 48.0 188² 30/25 7.5 265 G 0.72744.7 48.5 203² 30/26 7.8 265 H 0.645 44.0 51.0  55² 7.5/8   6.9 265 I0.605 43.3 48.6  55² 7.5/8   6.9 265 J 0.711 46.1 48.6 196² 20/17 11.5275 K 0.721 45.8 48.8 193² 20/17 11.4 275 1 butyltintris-2-ethylhexanoate was used as the source of tin ²dimethyl tin oxidewas used as the source of tin ³dibutyl tin oxide was used as the sourceof tin

The data in Table 15 shows that the stability of polymer melts can beenhanced by modifying process conditions such as final polymerizationtemperature, rate of vacuum being created in the reaction vessel, thetime under vacuum, among other, as reported below. The melt levelstability and the visual grading reported in Table 15 are based on thescales disclosed in Example 25.

TABLE 15 Properties of the polyesters of Example 26 Polymer % foamVisual grading Melt level color in of Example L* a* b* stabilityobservations polyester polyester A 83.55 −0.93 2.44 2 Slight yellow 30%4 tint B 84.39 −1.48 3.89 1 Good color: 29% 4 No yellow tint C 84.46−0.98 1.82 1 Slight yellow 21% 2 tint D 86.30 −0.75 1.27 1 Good color:17% 2 No yellow tint E 85.60 −1.20 2.68 3 Yellow tint 38% 4 F 83.88−0.97 1.64 1 Slight yellow 12% 1 tint G 85.76 −0.92 2.03 1 Slight yellow12% 2 tint H 84.40 −0.98 1.61 1 Good color: NM 1 No yellow tint I 84.88−0.63 0.99 1 Slight yellow 11% 1 tint J 85.01 −1.02 1.77 1 Slight yellow18% 3 tint K 84.13 −0.93 1.56 1 Slight yellow 25% 4 tint NM = notmeasured

Example 26A

A 500 ml round bottom flask was charged with 0.4 moles of DMT (77.6grams), 0.224 moles of CHDM (32.3 grams), 0.256 moles of TMCD (36.8grams), and 0.0460 grams of dibutyl tin oxide. The flask was equippedwith a stainless steel stirrer and polymer head that allowed bothnitrogen purge and vacuum capabilities. The flask was immersed in aBelmont metal bath at 200° C. and stirred at 25 RPM until the contentsmelted. The stirring was increased to 200 RPM and these conditions wereheld for 3 hours and 15 minutes. The temperature was increased to 220°C. and these conditions held for an additional 30 minutes. Thetemperature was increased to 290° C. over 20 minutes. After 290° C. wasobtained, the pressure was reduced from atmosphere to a set point (SP)of 0.3 over 15 minutes. Stirring was decreased as the viscosityincreased to a minimum of 15 RPM. The lowest vacuum reading measured was0.70 (even though the SP was 0.3) and the total time under vacuum was 30minutes.

The rest of the polyesters of this example were prepared in a 500 mlround bottom flask fitted with a stirrer and a polymer head that allowedboth a nitrogen purge and vacuum when necessary. Raw materials wereweighed into the flask for a 0.4 mole run (polymer repeat unit=274grams/mole): 0.400 moles of DMT (77.6 grams), 0.224 moles of CHDM (32.3grams) and 0.256 moles of TMCD (36.8 grams) and 0.112 g butyltintris-2-ethylhexanoate, 0.0314 g dimethyl tin oxide, or 0.0460 g dibutyltin oxide (as reported in Table 14). These values assume a targetconcentration of 200 ppm Sn in the final polymer and were adjustedaccordingly for other target concentrations. The actual tinconcentration for each polyester in this example is reported in Table 14

The glycol/acid ratio for all but two runs in this example was 1.2/1with the excess being 2% CHDM and the rest of the 20% excess being TMCD.The glycol/acid ratio for Example 26H was 1.1/1, with the excess beingTMCD. The glycol/acid ratio for Example 261 was 1.05/1, with the excessbeing TMCD. The catalyst was weighed into the flask, either as a solidor liquid. Triphenyl phosphate was weighed into the flask as a solid inthe amounts recited in Table 14. The TPP in Example 26K was added latefrom a methanol solution.

The set points and data collection were facilitated by a Camile processcontrol system. Once the reactants were melted, stirring was initiatedand slowly increased as indicated below in the corresponding Camilesequences. The temperature of the reactor also gradually increased withrun time.

The ester exchange and polycondensation reactions were carried out inthe same 500 ml flask. The temperature/pressure/stir rate sequencecontrolled by the Camile software for each example is reported in thefollowing tables. The final polymerization temperature (Pz Temp.) forthe experiments of this Example ranged from 265° C. to 290° C. and isreported in Table 14.

Temperature, Stage Time (minutes) C. Vacuum (torr) Stirring (RPM) CamileSequence for Example 26B to Example 26D 1 3 200 760 0 2 0.1 200 760 25 32 200 760 25 4 0.1 200 760 100 5 1 200 760 100 6 0.1 200 760 200 7 90200 760 200 8 0.1 210 760 200 9 120 210 760 200 10 5 245 760 50 11 32250 375 50 12 30 255 375 50 13 3 255 50 50 14 30 260 50 50 15 3 265 1525 16 110 265 15 25 17 3 270 2 25 18 110 275 2 25 19 2 275 400 0 20 1275 760 0 Camile Sequence for Example 26E 1 3 200 760 0 2 0.1 200 760 253 2 200 760 25 4 0.1 200 760 100 5 1 200 760 100 6 0.1 200 760 200 7 90200 760 200 8 0.1 210 760 200 9 120 210 760 200 10 5 245 760 50 11 3 245375 50 12 30 245 375 50 13 3 250 20 50 14 30 250 20 50 15 3 255 5 25 16110 255 5 25 17 3 265 1 25 18 110 265 1 25 19 2 265 400 0 20 1 265 760 0Camile Sequence for Example 26F and Example 26G Viscosity constrainedsequence, low vacuum 1 3 200 760 0 2 0.1 200 760 25 3 2 200 760 25 4 0.1200 760 100 5 1 200 760 100 6 0.1 200 760 200 7 90 200 760 200 8 0.1 210760 200 9 120 210 760 200 10 5 245 760 50 11 3 245 375 50 12 30 245 37550 13 3 250 20 50 14 30 250 20 50 15 3 255 5 25 16 110 255 5 25 17 3 2650.2 25 18 110 265 0.2 25 19 2 265 400 0 20 1 265 760 0 Camile Sequencefor Example 26H and Example 26I Viscosity constrained sequence, lowvacuum 1 3 200 760 0 2 0.1 200 760 25 3 2 200 760 25 4 0.1 200 760 100 51 200 760 100 6 0.1 200 760 200 7 90 200 760 200 8 0.1 210 760 200 9 120210 760 200 10 5 245 760 50 11 3 245 375 50 12 30 245 375 50 13 3 250 2050 14 30 250 20 50 15 3 255 3 25 16 110 255 3 25 17 3 265 1 25 18 110265 1 25 19 2 265 400 0 20 1 265 760 0 Camile Sequence for Example 26Jand Example 26K 1 3 200 760 0 2 0.1 200 760 25 3 2 200 760 25 4 0.1 200760 100 5 1 200 760 100 6 0.1 200 760 200 7 90 200 760 200 8 0.1 210 760200 9 120 210 760 200 10 5 245 760 50 11 3 245 375 50 12 30 245 375 5013 3 250 20 50 14 30 250 20 50 15 3 260 5 25 16 110 260 5 25 17 3 275 125 18 110 275 1 25 19 2 275 400 0 20 1 275 760 0

Example 27

This example illustrates the preparation of polyesters utilizingdifferent thermal stabilizers and showing their effect on the stabilityof the polyester melts during processing.

A variety of polyesters were prepared as described below from 100 mole %DMT, and different concentrations of CHDM, and TMCD. The mole % of TMCDfor the experiments of this example is reported in Table 16 below, withthe glycol balance being CHDM. The DMT, CHDM, and TMCD were of the sameorigin as in Example 25. The catalyst was either dimethyltin oxide(Strem Chemical Co., Batch B4058112) or butyltin-tris-2-ethylhexonate(Aldrich, Batch 06423CD). The thermal stabilizer is indicated in Table16 and was chosen from Merpol A (an octyl alcohol phosphate estermixture from DuPont), triethylphosphate (Aldrich), Irgafos 168(tris(2,4-di-tert-butylphenyl)phosphate, Ciba Specialty Chemicals),Doverphos 9228 (CAS# 154862-43-8, bis(2,4-dicumylphenyl) pentaerythritoldiphosphite, Dover), Weston 619 g (CAS# 85190-63-2,2-propanol,1,1′,1″-nitrilotris-, mixt. with3,9-bis(octadecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane,GE SC), triphenylphosphine oxide (Aldrich), triphenylphosphate (Aldrichor FERRO), NaH₂PO₄ (Aldrich), Zn₃(PO₄)₂ (Aldrich), and H₃PO₄ (Aldrich).Unless otherwise indicated in Table 16, the source of phosphorous wasadded upfront, with the rest of the polyester reagents. The cis/transratio of the CHDM was as described above while the cis/trans ratio ofthe TMCD is reported in Table 16.

TABLE 16 Composition and inherent viscosity for the polyesters ofExample 27 P Sn/P Final Melt TMCD (ppm) actual Pz IV (mole TMCD Sn theo/wt Temp Example (dL/g) %) % cis (ppm) meas ratio (° C.) A 0.564 45.749.7 211² 28/26 8.1 265 B 0.167 29.2 58.2 218² 28/39 5.6 265 C 0.64745.2 49.2 195² 20/19 10.3 265 D 0.674 46.3 48.7 196² 20/18 10.9 265 E0.700 45.6 49.4 195² 20/0  * 265 F 0.738 45.9 49.0 214² 20/8  26.8 265 G0.672 46.4 49.7 192² 20/11 17.5 265 H 0.714 46.0 48.5 189² 20/7  27.0265 I 0.73 42.3 45.1 212¹ 0 * 265 J 0.58 44.4 44.5 209¹ 28/27 7.7 265 K0.53 43.4 45.0 213¹ 28/28 7.6 265 L 0.69 44.3 44.4 209¹ 28/20 10.5 265 M0.61 43.7 45.4 211¹ 28/25 8.4 265 N 0.76 43.9 44.4 200¹ 28/20 10.0 265 O0.66 44.6 44.3  58¹ 0 * 265 P 0.6 42.4 44.7  60¹ 7/7 8.6 265 Q 0.5 42.945.4  57¹ 7/7 8.1 265 R 0.51 43.8 45.1  52¹ 200/55⁴  0.9 265 S 0.64 44.044.4  58¹ 200/71⁴  0.8 265 ¹butyltin tris-2-ethylhexanoate was used asthe source of tin ²dimethyl tin oxide was used as the source of tin 3dibutyl tin oxide was used as the source of tin ⁴polymer was hazy due toinsolubles

The data in Table 17 shows the stability of polymer melts usingdifferent sources of phosphorous as thermal stabilizers. Example 27B,while outside the scope of the originally-filed claims with respect tomole % TMCD, is included here to show the use of phosphoric acid as athermal stabilizer. The data shows that phosphate esters and phosphorouscompounds that can be hydrolyzed to phosphate esters provide stable meltand acceptable polyester products. The melt level stability and thevisual grading reported in Table 17 are based on the scales disclosed inExample 25.

TABLE 17 Properties of the polyesters of Example 27 Visual Melt Polymergrading Phosphorus level color % foam in of Example L* a* b* sourcestability observations polyester polyester A 83.87 −1.09 1.61 Merpol A 1NM NM NM B NM NM NM H₃PO₄ 1 Good color:  7% 1 No yellow tint C 84.84−0.94 1.40 Merpol A 1 Good color: 22% 3 No yellow tint D 85.86 −0.691.07 Merpol A 1 Slight yellow 21% 3 added after tint EE E 83.77 −1.121.91 Triethyl 2 Slight yellow 25% 4 phosphate tint F 84.05 −2.06 8.66Triethyl 2 Brownish- 22% 4 phosphate yellow tint G 77.63 −0.82 3.33Irgafos 168 3 NM NM NM H 78.68 −0.83 3.34 Irgafos 168 3 Brownish- 24% 4added after yellow tint EE I NM NM NM none NN Slight yellow 26% 4 tint JNM NM NM Doverphos NN Good color: 21% 3 9228 No yellow tint K NM NM NMDoverphos NN NM NM NM 9228 L NM NM NM Weston 619 g NN Good color: 21% 4No yellow tint M NM NM NM Triphenyl NN Slight yellow 14% 2 phosphatetint N NM NM NM Triphenyl NN Slight yellow 23% 3 phosphine tint oxide ONM NM NM none NN Slight yellow 19% 2 tint P NM NM NM Triphenyl NN NM NMNM phosphate Q NM NM NM Triphenyl NN Good color: 10% 1 phosphate Noyellow tint R NM NM NM NaH₂PO₄ NN Good color: 17% 1 No yellow tint S NMNM NM Zn₃(PO₄)₂ NN Good color: 16% 2 No yellow tint EE = ester exchange;NM = not measured; NN = nor noted The sample of Example R was hazy sovisual grading may have been impaired

Example 27A to Example 27H

These polyesters were prepared as follows. A mixture of 77.6 g (0.4 mol)dimethyl terephthalate, 32.3 g (0.224 mol) 1,4-cyclohexanedimethanol,36.8 g (0.256 mol) 2,2,4,4-tetramethyl-1,3-cyclobutanediol was placed ina 500-ml flask equipped with an inlet for nitrogen, a metal stirrer, anda short distillation column. The catalyst was also added to the reactionflask. The amount and type of catalyst are in detailed in Table 16. Thephosphorus compounds were also added to the reaction flask. Thetheoretical and measured amount of phosphorus compound for eachexperiment in this example is detailed in Table 16. The flask was placedin a Wood's metal bath already heated to 200° C. Thetemperature/pressure/stir rate sequence were controlled by the Camilesoftware for each experiment and is reported below. In some cases, wherenoted (Example 27D and Example 27H), the phosphorus additive was addedafter ester exchange. This corresponds to the end of stage 9 in thecorresponding Camile sequence.

Example 271 to Example 27S

These polyesters were prepared as follows. A mixture of 77.6 g (0.4 mol)dimethyl terephthalate, 33.31 g (0.231 mol) 1,4-cyclohexanedimethanol,35.91 g (0.249 mol) 2,2,4,4-tetramethyl-1,3-cyclobutanediol was placedin a 500-ml flask equipped with an inlet for nitrogen, a metal stirrer,and a short distillation column. The catalyst was also added to thereaction flask. The amount and type of catalyst are in detailed in Table16. The source of phosphorous was weighed into the flask in the amountsrecited in Table 16, which includes the theoretical and measured amountof phosphorus compound for each experiment. The flask was placed in aWood's metal bath already heated to 200° C. Thetemperature/pressure/stir rate sequence controlled by the Camilesoftware for each example is reported below.

The glycol/acid ratio for all experiments in this example was 1.2/1 withthe excess being 2% CHDM and the rest of the 20% excess being TMCD. Thecatalyst was weighed into the flask, either as a solid or liquid.

The set points and data collection were facilitated by a Camile processcontrol system. Once the reactants were melted, stirring was initiatedand slowly increased as indicated below in the corresponding Camilesequences. The temperature of the reactor also gradually increased withrun time.

The temperature/pressure/stir rate sequence controlled by the Camilesoftware for each example is reported in the following tables. The finalpolymerization temperature (Pz Temp.) for the experiments of thisexample was 265° C.

Temperature, Stage Time (minutes) C. Vacuum (torr) Stirring (RPM) CamileSequence for Example 27A and Example 27B Viscosity constrained sequence1 3 200 760 0 2 0.1 200 760 25 3 2 200 760 25 4 0.1 200 760 100 5 1 200760 100 6 0.1 200 760 200 7 90 200 760 200 8 0.1 210 760 200 9 120 210760 200 10 0.1 220 760 200 11 30 220 760 200 12 5 245 760 50 13 3 245375 50 14 30 245 375 50 15 3 250 20 50 16 30 250 20 50 17 3 255 3 25 18110 255 3 25 19 3 265 1 25 20 110 265 1 25 Camile Sequence for Example27C to Example 27S Viscosity constrained sequence, low vacuum 1 3 200760 0 2 0.1 200 760 25 3 2 200 760 25 4 0.1 200 760 100 5 1 200 760 1006 0.1 200 760 200 7 90 200 760 200 8 0.1 210 760 200 9 120 210 760 20010 5 245 760 50 11 3 245 375 50 12 30 245 375 50 13 3 250 20 50 14 30250 20 50 15 3 255 3 25 16 110 255 3 25 17 3 265 1 25 18 110 265 1 25 192 265 400 0 20 1 265 760 0

Example 28

This example illustrates the preparation of polyesters at a pilot plantscale comprising at least one thermal stabilizer, reaction productsthereof, and mixtures thereof, resulting in improved stability of thepolyester melts during processing.

A variety of polyesters were prepared as described below from 100 mole %DMT, CHDM, and TMCD. The mole % of TMCD for the experiments of thisexample is reported in Table 18 below, with the glycol balance beingCHDM. The DMT, CHDM, and TMCD were of the same origin as in Example 25.The catalyst was either dimethyltin oxide (Strem Chemical Co., BatchB4058112) or butyltin-tris-2-ethylhexonate (Aldrich, Batch 06423CD). Thethermal stabilizer was triphenyl phosphate (TPP) (Aldrich). Unlessotherwise indicated below, the source of phosphorous was added upfront,with the rest of the polyester reagents. The cis/trans ratio of the CHDMwas as described above while the cis/trans ratio of the TMCD is reportedin Table 18.

TABLE 18 Composition and inherent viscosity for the polyesters ofExample 28 Melt Ex- IV TMCD P am- (dL/ (mole TMCD Sn (ppm) ple g) %) %cis (ppm) theo L* a* b* A 0.553 46.1 45.8 228² 300 80.50 −1.51 4.27 B0.620 46.0 46.0 204¹ 100 83.42 −1.18 4.92 C 0.613 45.1 46.3 193¹ 10077.60 −1.80 4.85 D 0.624 45.4 46.2 209² 100 79.69 −1.71 6.45 ¹butyltintris-2-ethylhexanoate was used as the source of tin ²dimethyl tin oxidewas used as the source of tin

Example 28A

84.96 lbs (198.83 gram-mol) dimethyl terephthalate, 35.38 lbs (111.54gram-mol) 1,4-cyclohexanedimethanol, 40.30 lbs (127.06 gram-mol)2,2,4,4-tetramethyl-1,3-cyclobutanediol were reacted together in thepresence of 200 ppm of dimethyltin oxide as tin catalyst and 300 ppmtriphenylphosphate (16.35 grams). The reaction was carried out under anitrogen gas purge in an 74-gallon stainless steel pressure vessel whichwas fitted with a condensing column, a vacuum system, and aHELICONE-type agitator. With the agitator running at 25 RPM, thereaction mixture temperature was increased to 250° C. and the pressurewas increased to 20 psig. The reaction mixture was held for 2 hours at250° C. and 20 psig pressure. The pressure was then decreased to 0 psigat a rate of 3 psig/minute. The agitator speed was then decreased to 15RPM, the temperature of the reaction mixture was then increased to 270°C., and the pressure was decreased to <1-mm. The reaction mixture washeld at 270° C. and a pressure of <1 mm of Hg for 3.75 hours. Thepressure of the vessel was then increased to 1 atmosphere using nitrogengas. The molten polymer was then extruded from the pressure vessel usingan extrusion die. The extruded polymer strands were then pulled througha cold water bath to cool them after which the strands were pelletized.The pelletized polymer had an inherent viscosity of 0.553. NMR analysisshowed that the polymer was composed of 53.9 mol %1,4-cyclohexanedimethanol moiety and 46.1 mol %2,2,4,4-tetramethyl-1,3-cyclobutanediol moiety. The polymer had colorvalues of: L*=80.50, a*=−1.51, and b*=4.27.

Example 28B to Example 28D were prepared in a similar manner to Example28A, having the composition disclosed in Table 18.

Example 28E represents PCTG Eastar DN001 from Eastman Chemical Company,having an IV of 0.73 dL/g with a nominal composition of 100 mole %terephthalic acid residues, 62 mole % CHDM residues and 38 mole %ethylene glycol residues. Example 28F represents the polycarbonateMakrolon 2608 from Bayer, with a nominal composition of 100 mole %bisphenol A residues and 100 mole % diphenyl carbonate residues. Example28G represents an Eastman Chemical Company polyester, with a nominalcomposition of 100 mole % terephthalic acid residues, 55 mole % CHDMresidues and 45 mole % TMCD residues. Example 28H represents PETG Eastar6763 from Eastman Chemical Company, with a nominal composition of 100mole % terephthalic acid, 31 mole % cyclohexanedimenthanol (CHDM) and 69mole % ethylene glycol.

Example 28I

The polyester of Example 28I is a blend of 10 different polyesters, eachprepared in the following manner. 84.96 lbs (198.83 gram-mol) dimethylterephthalate were reacted in the presence of 200 ppm of tin catalyst(as butyltin-tris-ethylhexanoate) with 50.45 to 51.46-lbs (159.06 162.24gram-mol, depednign on the batch) 1,4-cyclohexanedimethanol and 24.22 to31.53-lbs (76.36 to 99.41 gram-mol, also depending on the batch)2,2,4,4-tetramethyl-1,3-cyclobutanediol. The reaction was carried outunder a nitrogen gas purge in an 74-gallon stainless steel pressurevessel fitted with a condensing column, a vacuum system, and aHELICONE-type agitator, to provide glycol/dimethyl terephthalate molarratios of 1.2/1 to 1.3/1. With the agitator running at 25 RPM, thereaction mixture temperature was increased to 250° C. and the pressurewas increased to 20 psig. The reaction mixture was held for 2 hours at250° C. and 20 psig pressure. The pressure was then decreased to 0 psigat a rate of 3 psig/minute. The agitator speed was then decreased to 15RPM, the temperature of the reaction mixture was then increased to260-270° C., and the pressure was decreased to 90 mm of Hg. The reactionmixture was held at 260-270° C. and 90-mm pressure for 1 hour. Thetemperature of the reaction mixture was then increased to 275-290° C.and the pressure was decreased to <1 mm of Hg. The reaction mixture washeld at 275-290° C. and <1 mm of Hg for 1.5-3 hours to complete thepolycondensation stage. The pressure of the pressure vessel was thenincreased to 1 atmosphere using nitrogen gas. The molten polymer wasthen extruded from the pressure vessel into a cold water bath. Thecooled, extruded polymer was ground to pass a 6-mm screen.

Ten separate batches were prepared using the above procedure. Thefollowing table contains the NMR compositions, IV values, and colorvalues that were obtained on the 10 batches. The final polyester blendhad an IV of 0.63 dL/g, 100 mole % terephthalic acid residues and atarget of 20 mole % TMCD residues and 80 mole % CHDM residues.

Target % TMCD by IV Color Batch Composition NMR (dL/g) L* a* b* 1 20%TMCD; 16.8 0.665 73.95 −0.61 10.31 80% CHDM 2 20% TMCD; 17.5 0.691 70.48−0.49 10.68 80% CHDM 3 20% TMCD; 16.4 0.650 71.14 −0.68 10.16 80% CHDM 420% TMCD; 22.2 0.685 79.80 −1.80 7.43 80% CHDM 5 20% TMCD; 24.9 0.66874.47 −1.11 7.83 80% CHDM 6 20% TMCD; 22.6 0.705 67.94 1.28 26.91 80%CHDM 7 20% TMCD; 22.1 0.627 72.43 0.41 22.68 80% CHDM 8 20% TMCD; 25.30.712 76.70 0.41 10.73 80% CHDM 9 20% TMCD; 23.5 0.697 74.21 0.79 15.2380% CHDM 10 20% TMCD; 25.3 0.724 73.55 −0.61 9.52 80% CHDM

Plaques (4 inch×4 inch×⅛ inch thick) were prepared in a Toyo 110injection molding press from the polyesters of Table 18. Pellets of eachpolyester were feed into the press and heated to the temperaturesreported in Table 19. The residence time of the molten polymer in thebarrel before injection is also reported in Table 19. Once the part hadcooled sufficiently, it was visually analyzed and the splay generatedduring the injection molding process was recorded.

The data in Table 19 shows the effect of molding conditions on splaygeneration in injection-molded plaques made out of the polyesters inTable 18.

TABLE 19 Splay generation in molded parts made out of the polyesters ofExample 28 Temp Setpoint, Residence Splay in part made out of polyesterin Table 18 ° F. Time, min A B C D E F G 520 0.47 0 0 0 0 0 0 0 (271°C.) 1.02 0 0 0 0 0 0 0 1.59 0 0 0 0 0 0 0 2.7 0 0 0 0 0 0 0 4.94 0 0 0 00 0 0 9.4 0 0 0 0 0 0 1 550 0.47 0 0 0 0 0 0 0 (288° C.) 1.02 0 0 0 0 00 0 1.59 0 0 0 0 0 0 0 2.7 0 0 0 0 0 0 0 4.94 0 0 0 0 0 0 1 9.4 0 1 1 10 0 2-3 580 0.47 0 0 0 0 0 0 0 (304° C.) 1.02 0 0 0 0 0 0 0 1.59 0 0 0 00 0 1 2.7 0 0 1 0 0 0 1-2 4.94 0 1-2 1-2 1-2 0 0 2-3 9.4 1-2 2-3 2-3 2-31-2 0 3 610 0.47 0 0 0 0 NA NA NA (321° C.) 1.02 0 0 0 0 NA NA NA 1.59 00 0 0 NA NA NA 2.7 0 1-2 1-2 1-2 NA NA NA 4.94 1-3 2-3 2-3 2-3 NA NA NA9.4 3 3 3 3 NA NA NA Splay Ratings: none (0), light (1), moderate (2),heavy (3); NA = not available

The data in Table 20 shows the quality of films made out of thepolyesters in Table 18.

The polymers were extruded on a 1.5″ Killion extruder using a GeneralPurpose screw. The polymers were extruded at temperatures of 572° F.(300° C.) and 527° F. (275° C.). The following extruder conditions wereused for each polymer in the 572° F. extrusions:

Chill Clamp Pres- Screw Roll Sam- Zone Die Adapter Ring Melt sure SpeedSpeed ple Temp Temp Temp Temp Temp (PSI) (RPM) (RPM) 1 572 572 572 572612 1200 70 4.3 2 572 572 572 572 619 1450 35 2.2 3 572 572 572 572 6182500 105 7.2

The following extruder conditions were used for each polymer in the 527°F. extrusions:

Chill Clamp Pres- Screw Roll Sam- Zone Die Adapter Ring Melt sure SpeedSpeed ple Temp Temp Temp Temp Temp (PSI) (RPM) (RPM) 1 527 527 527 527569 1600 70 4.2 2 527 527 527 527 565 900 35 2.3 3 527 527 527 527 5712200 105 7.2

TABLE 20 Quality of films made out of the polyesters of Example 28Extrusion Example Conditions A B C D H I 275° C.: 35 RPM 1 2 2 2 1 4275° C.; 70 RPM 1 2 2 2 1 3 275° C.; 105 RPM 1 1 2 2 1 3 300° C.: 35 RPM2 3 3 3 1 4 300° C.; 70 RPM 1 2 3 2 1 4 300° C.; 105 RPM 1 2 2 1 1 4Rating Key Rating Good film quality; no visual 1 bubbles were observedexiting the die or in melt bank: nice film, very difficult to visuallydetect bubbles. Good film quality; occasional 2 bubbles observed leavingthe die; bubbles in the film are visually easier to detect but sparse.Mediocre film quality; bubbles 3 are easily seen leaving the die lipsand are very evident in the finished film. Very poor film quality;bubbles 4 evident in the melt bank and exiting the die lips; very poorcolor.

It can be clearly seen from a comparison of the data in the aboverelevant working examples that the polyesters of the present inventionoffer an advantage over the commercially available polyesters withregard to at least one of bubbling, splaying, color formation, foaming,off-gassing, and erratic melt levels in the polyester's production andprocessing systems.

The invention has been described in detail with reference to theembodiments disclosed herein, but it will be understood that variationsand modifications can be effected within the spirit and scope of theinvention.

1. A blow molded article of manufacture comprising a polyestercomposition comprising at least one polyester which comprises: (a) adicarboxylic acid component comprising: i) 80 to 100 mole % ofterephthalic acid residues; ii) 0 to 20 mole % of aromatic dicarboxylicacid residues having up to 20 carbon atoms; and iii) 0 to 10 mole % ofaliphatic dicarboxylic acid residues having up to 16 carbon atoms; and(b) a glycol component comprising: i) 20 to 30 mole % of2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and ii) 70 to 80 mole% of 1,4-cyclohexanedimethanol residues, wherein the total mole % of thedicarboxylic acid component is 100 mole %, and the total mole % of theglycol component is 100 mole %; wherein the inherent viscosity of saidpolyester is from 0.60 to 0.75 dL/g as determined in 60/40 (wt/wt)phenol/tetrachloroethane at a concentration of 0.5 g/100 ml at 25° C.;wherein said polyester has a Tg of 100 to 130° C.; wherein saidpolyester has a notched Izod impact strength of at least 7.5 ft-lb/inchat 23° C. according to ASTM D256 with a 10-mil notch in a ⅛-inch thickbar; wherein the melt viscosity of said polyester is less than 10,000poise as measured at 1 radian/second on a rotary melt rheometer at 290°C.
 2. The article of claim 1, wherein the inherent viscosity is from0.65 to 0.75 dL/g.
 3. The article of claim 1, wherein the glycolcomponent comprises 25 to 30 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 70 to 75 mole %1,4-cyclohexanedimethanol residues.
 4. The article of claim 1, whereinthe glycol component of said polyester comprises 20 to 25 mole %2,2,4,4-tetramethyl-1,3-cyclobutanediol residues and 75 to 80 mole %1,4-cyclohexanedimethanol residues.
 5. The article of claim 1, whereinsaid polyester has a Tg of 100 to 120° C.
 6. The article of claim 1,wherein said polyester has a Tg of 105 to 120° C.
 7. The article ofclaim 1, wherein the dicarboxylic acid component comprises 90 to 100mole % of terephthalic acid residues.
 8. The article of claim 1, whereinsaid polyester comprises 1,3-propanediol residues, 1,4-butanediolresidues, or mixture thereof.
 9. The article of claim 1, wherein saidpolyester comprises from 0.01 to 15 mole % of ethylene glycol residues.10. The article of claim 1, wherein said2,2,4,4tetramethyl-1,3-cyclobutanediol is a mixture comprising greaterthan 50 mole % of cis-2,2,4,4-tetramethyl-1,3-cyclobutanediol and lessthan 50 mole % of trans-2,2,4,4-tetramethyl-1,3-cyclobutanediol.
 11. Thearticle of claim 1, wherein said 2,2,4,4tetramethyl-1,3-cyclobutanediolis a mixture comprising from 30 to 70 mole % ofcis-2,2,4,4-tetramethyl-1,3-cyclobutanediol and from 70 to 30 mole % oftrans-2,2,4,4-tetramethyl-1,3-cyclobutanediol.
 12. The article of claim1, wherein said 2,2,4,4tetramethyl-1,3-cyclobutanediol is a mixturecomprising from 40 to 60 mole % ofcis-2,2,4,4-tetramethyl-1,3-cyclobutanediol and from 60 to 40 mole % oftrans-2,2,4,4-tetramethyl-1,3-cyclobutanediol.
 13. The article of claim1, wherein said polyester composition comprises at least one polymerchosen from at least one of the following: poly(etherimides),polyphenylene oxides, poly(phenylene oxide)/polystyrene blends,polystyrene resins, polyphenylene sulfides, polyphenylenesulfide/sulfones, polysulfones; polysulfone ethers, andpoly(ether-ketones).
 14. The article of claim 1, wherein said polyestercomprises residues of at least one branching agent.
 15. The article ofclaim 33, wherein said polyester comprises residues of at least onebranching agent an amount of 0.01 to 10 mole % based on the total molepercentage of the diacid or diol residues.
 16. The article of claim 1,wherein said polyester has a crystallization half-time of greater than 5minutes at 170° C.
 17. The article of claim 1, wherein said polyestercomposition has a density of less than 1.2 g/ml at 23° C.
 18. Thearticle of claim 1, wherein said polyester composition comprises atleast one thermal stabilizer or reaction products thereof.
 19. Thearticle of claim 1, having a b* value of from −10 to less than 10 andthe L* values can be from 50 to 90 according to the L*, a* and b* colorsystem of the CIE (International Commission on Illumination).
 20. Thearticle of claim 1, wherein said polyester has a notched Izod impactstrength of at least 10 ft-lbs/in at 23° C. according to ASTM D256 witha 10-mil notch in a ⅛-inch thick bar.
 21. The article of claim 1,wherein the polyester comprises the residue of at least one catalystcomprising a tin compound or a reaction product thereof.
 22. The articleof claim 1 which is an extrusion blow molded article of manufacture. 23.A blow molded article of manufacture comprising a polyester compositioncomprising at least one polyester which comprises: (a) a dicarboxylicacid component comprising: i) 80 to 100 mole % of terephthalic acidresidues; ii) 0 to 20 mole % of aromatic dicarboxylic acid residueshaving up to 20 carbon atoms; and iii) 0 to 10 mole % of aliphaticdicarboxylic acid residues having up to 16 carbon atoms; and (b) aglycol component comprising: i) 20 to 30 mole % of2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and ii) 70 to 80 mole% of 1,4-cyclohexanedimethanol residues, wherein the total mole % of thedicarboxylic acid component is 100 mole %, and the total mole % of theglycol component is 100 mole %; wherein the inherent viscosity of saidpolyester is from 0.60 to 0.75 dL/g as determined in 60/40 (wt/wt)phenol/tetrachloroethane at a concentration of 0.5 g/100 ml at 25° C.;wherein said polyester has a Tg of 100 to 130° C.; wherein saidpolyester has a notched Izod impact strength of at least 7.5 ft-1b/inchat 23° C. according to ASTM D256 with a 10-mil notch in a ⅛-inch thickbar at 23° C.; wherein the melt viscosity of said polyester is less than10,000 poise as measured at 1 radian/second on a rotary melt rheometerat 290° C.; and wherein said polyester composition contains nopolycarbonate.
 24. The article of claim 23, wherein said polyester has aTg of 100 to 120° C.
 25. The article of claim 23, wherein said polyesterhas a Tg of 100 to 115° C.
 26. A blow molded article of manufacturecomprising a polyester composition comprising at least one polyesterwhich comprises: (a) a dicarboxylic acid component comprising: i) 80 to100 mole % of terephthalic acid residues; ii) 0 to 20 mole % of aromaticdicarboxylic acid residues having up to 20 carbon atoms; and iii) 0 to10 mole % of aliphatic dicarboxylic acid residues having up to 16 carbonatoms; and (b) a glycol component comprising: i) 20 to 30 mole % of2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and ii) 70 to 80 mole% of 1,4-cyclohexanedimethanol residues, iii) 0.01 to less than 15 mole% ethylene glycol residues; wherein the total mole % of the dicarboxylicacid component is 100 mole %, and the total mole % of the glycolcomponent is 100 mole %; wherein the inherent viscosity of saidpolyester is from 0.60 to 0.75 dL/g as determined in 60/40 (wt/wt)phenol/tetrachloroethane at a concentration of 0.5 g/100 ml at 25° C.;wherein said polyester has a Tg of 100 to 130° C.; wherein saidpolyester has a notched Izod impact strength of at least 7.5 ft-1b/inchat 23° C. according to ASTM D256 with a 10-mil notch in a ⅛-inch thickbar; wherein the melt viscosity of said polyester is less than 10,000poise as measured at 1 radian/second on a rotary melt rheometer at 290°C.
 27. A blow molded article of manufacture comprising a polyestercomposition comprising at least one polyester which comprises: (a) adicarboxylic acid component comprising: i) 80 to 100 mole % ofterephthalic acid residues; ii) 0 to 20 mole % of aromatic dicarboxylicacid residues having up to 20 carbon atoms; and iii) 0 to 10 mole % ofaliphatic dicarboxylic acid residues having up to 16 carbon atoms; (b) aglycol component comprising: i) 20 to 30 mole % of2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and ii) 70 to 80 mole% of 1,4-cyclohexanedimethanol residues, and (c) residues of at leastone branching agent in the amount of 0.01 to 10 mole % based on thetotal mole percentage of the diacid residues or diol residues; whereinthe total mole % of the dicarboxylic acid component is 100 mole %, andthe total mole % of the glycol component is 100 mole %; wherein theinherent viscosity of said polyester is from 0.60 to 0.75 dL/g asdetermined in 60/40 (wt/wt) phenol/tetrachloroethane at a concentrationof 0.5 g/100 ml at 25° C.; wherein said polyester has a Tg of 100 to130° C.; wherein said polyester has a notched Izod impact strength of atleast 7.5 ft-1b/inch at 23° C. according to ASTM D256 with a 10-milnotch in a ⅛-inch thick bar; wherein the melt viscosity of saidpolyester is less than 10,000 poise as measured at 1 radian/second on arotary melt rheometer at 290° C.; and wherein said polyester compositioncontains no polycarbonate.
 28. A blow molded article of manufacturecomprising a polyester composition comprising: (I) at least onepolyester which comprises: (a) a dicarboxylic acid component comprising:i) 80 to 100 mole % of terephthalic acid residues; ii) 0 to 20 mole % ofaromatic dicarboxylic acid residues having up to 20 carbon atoms; andiii) 0 to 10 mole % of aliphatic dicarboxylic acid residues having up to16 carbon atoms; and (b) a glycol component comprising: i) 20 to 30 mole% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and ii) 70 to 80mole % of 1,4-cyclohexanedimethanol residues; and (II) at least onethermal stabilizer or the reaction product thereof chosen from at leastone of phosphoric acid, phosphorous acid, phosphonic acid, phosphinicacid, phosphonous acid, or an ester or salt thereof; wherein the totalmole % of the dicarboxylic acid component is 100 mole %, and the totalmole % of the glycol component is 100 mole %; wherein the inherentviscosity of said polyester is from 0.60 to 0.75 dL/g as determined in60/40 (wt/wt) phenol/tetrachloroethane at a concentration of 0.5 g/100ml at 25° C.; wherein said polyester has a Tg of 100 to 130° C.; wherein said polyester has a notched Izod impact strength of at least 7.5ft-1b/inch at 23° C. according to ASTM D256 with a 10-mil notch in a⅛-inch thick bar; wherein the melt viscosity of said polyester is lessthan 10,000 poise as measured at 1 radian/second on a rotary meltrheometer at 290° C.
 29. The article of claim 28, wherein the polyestercomposition comprises residues from at least one branching agent in theamount of 0.01 to 10 mole % based on the total mole percentage of thediacid residues or diol residues.
 30. The article of claim 28, whereinthe polyester composition comprises at least one additive chosen fromcolorants, dyes, mold release agents, flame retardants, plasticizers,nucleating agents, UV stabilizers, glass fiber, carbon filaments,fillers, impact modifiers, and mixtures thereof.
 31. The article ofclaim 28, wherein the polyester comprises from 0.01 to 15 mole % ofethylene glycol residues.
 32. The article of claim 1, wherein thepolyester composition comprises at least one additive chosen fromcolorants, dyes, mold release agents, flame retardants, plasticizers,nucleating agents, UV stabilizers, glass fiber, carbon filaments,fillers, impact modifiers, and mixtures thereof.
 33. The article ofclaim 1, wherein said polyester has a notched Izod impact strength of atleast 18 ft-lbs/in at 23° C. according to ASTM D256 with a 10-mil notchin a ⅛-inch thick bar.
 34. The arti cle of claim 1, wherein the meltviscosity of said polyester is less than 6,000 poise as measured at 1radian/second on a rotary melt rheometer at 290° C.
 35. The article ofclaim 23, wherein said polyester has a notched Izod impact strength ofat least 10 ft-lbs/in at 23° C. according to ASTM D256 with a 10-milnotch in a ⅛-inch thick bar.
 36. The article of claim 23, wherein themelt viscosity of said polyester is less than 6,000 poise as measured at1 radian/second on a rotary melt rheometer at 290°